Organic electroluminescent materials and devices

ABSTRACT

Novel ligands for metal complexes containing five-membered ring fused on pyridine or pyrimidine ring combined with partially fluorinated side chains exhibiting improved external quantum efficiency and lifetime are disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a non-provisional U.S. patent application claimingpriority, under 35 U.S.C. §119(e)(1), to U.S. Patent Application Ser.No. 62/161,948, filed on May 15, 2015, the entire contents of which areincorporated herein by reference.

PARTIES TO A JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connectionwith one or more of the following parties to a joint universitycorporation research agreement: The Regents of the University ofMichigan. Princeton University, University of Southern California, andthe Universal Display Corporation. The agreement was in effect on andbefore the date the claimed invention was made, and the claimedinvention was made as a result of activities undertaken within the scopeof the agreement.

FIELD OF THE INVENTION

The present invention relates to compounds for use as emitters, anddevices, such as organic light emitting diodes, including the same.

BACKGROUND

Opto-electronic devices that make use of organic materials are becomingincreasingly desirable for a number of reasons. Many of the materialsused to make such devices are relatively inexpensive, so organicopto-electronic devices have the potential for cost advantages overinorganic devices. In addition, the inherent properties of organicmaterials, such as their flexibility, may make them well suited forparticular applications such as fabrication on a flexible substrate.Examples of organic opto-electronic devices include organic lightemitting diodes/devices (OLEDs), organic phototransistors, organicphotovoltaic cells, and organic photodetectors. For OLEDs, the organicmaterials may have performance advantages over conventional materials.For example, the wavelength at which an organic emissive layer emitslight may generally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage isapplied across the device. OLEDs are becoming an increasinglyinteresting technology for use in applications such as flat paneldisplays, illumination, and backlighting. Several OLED materials andconfigurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full colordisplay. Industry standards for such a display call for pixels adaptedto emit particular colors, referred to as “saturated” colors. Inparticular, these standards call for saturated red, green, and bluepixels. Alternatively the OLED can be designed to emit white light. Inconventional liquid crystal displays emission from a white backlight isfiltered using absorption filters to produce red, green and blueemission. The same technique can also be used with OLEDs. The white OLEDcan be either a single EML device or a stack structure. Color may bemeasured using CIE coordinates, which are well known to the art.

One example of a green emissive molecule is tris(2-phenylpyridine)iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond fromnitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as wellas small molecule organic materials that may be used to fabricateorganic opto-electronic devices. “Small molecule” refers to any organicmaterial that is not a polymer, and “small molecules” may actually bequite large. Small molecules may include repeat units in somecircumstances. For example, using a long chain alkyl group as asubstituent does not remove a molecule from the “small molecule” class.Small molecules may also be incorporated into polymers, for example as apendent group on a polymer backbone or as a part of the backbone. Smallmolecules may also serve as the core moiety of a dendrimer, whichconsists of a series of chemical shells built on the core moiety. Thecore moiety of a dendrimer may be a fluorescent or phosphorescent smallmolecule emitter. A dendrimer may be a “small molecule,” and it isbelieved that all dendrimers currently used in the field of OLEDs aresmall molecules.

As used herein, “top” means furthest away from the substrate, while“bottom” means closest to the substrate. Where a first layer isdescribed as “disposed over” a second layer, the first layer is disposedfurther away from substrate. There may be other layers between the firstand second layer, unless it is specified that the first layer is “incontact with” the second layer. For example, a cathode may be describedas “disposed over” an anode, even though there are various organiclayers in between.

As used herein, “solution processible” means capable of being dissolved,dispersed, or transported in and/or deposited from a liquid medium,either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed thatthe ligand directly contributes to the photoactive properties of anemissive material. A ligand may be referred to as “ancillary” when it isbelieved that the ligand does not contribute to the photoactiveproperties of an emissive material, although an ancillary ligand mayalter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled inthe art, a first “Highest Occupied Molecular Orbital” (HOMO) or “LowestUnoccupied Molecular Orbital” (LUMO) energy level is “greater than” or“higher than” a second HOMO or LUMO energy level if the first energylevel is closer to the vacuum energy level. Since ionization potentials(IP) are measured as a negative energy relative to a vacuum level, ahigher HOMO energy level corresponds to an IP having a smaller absolutevalue (an IP that is less negative). Similarly, a higher LUMO energylevel corresponds to an electron affinity (EA) having a smaller absolutevalue (an EA that is less negative). On a conventional energy leveldiagram, with the vacuum level at the top, the LUMO energy level of amaterial is higher than the HOMO energy level of the same material. A“higher” HOMO or LUMO energy level appears closer to the top of such adiagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled inthe art, a first work function is “greater than” or “higher than” asecond work function if the first work function has a higher absolutevalue. Because work functions are generally measured as negative numbersrelative to vacuum level, this means that a “higher” work function ismore negative. On a conventional energy level diagram, with the vacuumlevel at the top, a “higher” work function is illustrated as furtheraway from the vacuum level in the downward direction. Thus, thedefinitions of HOMO and LUMO energy levels follow a different conventionthan work functions.

More details on OLEDs, and the definitions described above, can be foundin U.S. Pat. No. 7,279,704, which is incorporated herein by reference inits entirety.

SUMMARY

According to some embodiments of the present disclosure, a compoundcomprising a ligand L_(A) of Formula I,

wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclicring;

wherein R is fused to ring B and has a structure of Formula II:

wherein the wave lines indicate bonds to ring B;

wherein R¹ represents mono, di, tri, or tetra substitution, or nosubstitution;

wherein R² represents mono or di substitution, or no substitution;

wherein X¹, X², X³, and X⁴ are each independently carbon or nitrogen;

wherein at least two adjacent of X¹, X², X³, and X⁴ are carbon and fuseto R;

wherein X is selected from the group consisting of BR′, NR′, PR′, O, S,Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″;

wherein R¹, R², R³, R⁴, R′, and R″ are each independently selected fromthe group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof; and wherein any twoadjacent substituents are optionally joined to form into a ring;

wherein at least one of R³ and R⁴ comprises a chemical group selectedfrom the group consisting of alkyl, cycloalkyl, partially fluorinatedalkyl, partially fluorinated cycloalkyl, and combinations thereof;

wherein the ligand L_(A) is coordinated to a metal M;

wherein the ligand L_(A) is optionally linked with other ligands tocomprise a tridentate, tetradentate, pentadentate, or hexadentateligand; and

wherein M is optionally coordinated to other ligands is disclosed.

According to some embodiments, a first OLED comprising an anode, acathode, and an organic layer, disposed between the anode and thecathode, comprising a compound comprising a ligand L_(A) of Formula I isdisclosed.

According to some embodiments, a formulation comprising a compoundcomprising a ligand L_(A) of Formula I is also disclosed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does nothave a separate electron transport layer.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed betweenand electrically connected to an anode and a cathode. When a current isapplied, the anode injects holes and the cathode injects electrons intothe organic layer(s). The injected holes and electrons each migratetoward the oppositely charged electrode. When an electron and holelocalize on the same molecule, an “exciton,” which is a localizedelectron-hole pair having an excited energy state, is formed. Light isemitted when the exciton relaxes via a photoemissive mechanism. In somecases, the exciton may be localized on an excimer or an exciplex.Non-radiative mechanisms, such as thermal relaxation, may also occur,but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from theirsinglet states (“fluorescence”) as disclosed, for example, in U.S. Pat.No. 4,769,292, which is incorporated by reference in its entirety.Fluorescent emission generally occurs in a time frame of less than 10nanoseconds.

More recently. OLEDs having emissive materials that emit light fromtriplet states (“phosphorescence”) have been demonstrated. Baldo et al.,“Highly Efficient Phosphorescent Emission from OrganicElectroluminescent Devices,” Nature, vol. 395, 151-154, 1998;(“Baldo-I”) and Baldo et al., “Very high-efficiency green organiclight-emitting devices based on electrophosphorescence.” Appl. Phys.Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated byreference in their entireties. Phosphorescence is described in moredetail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporatedby reference.

FIG. 1 shows an organic light emitting device 100. The figures are notnecessarily drawn to scale. Device 100 may include a substrate 110, ananode 115, a hole injection layer 120, a hole transport layer 125, anelectron blocking layer 130, an emissive layer 135, a hole blockinglayer 140, an electron transport layer 145, an electron injection layer150, a protective layer 155, a cathode 160, and a barrier layer 170.Cathode 160 is a compound cathode having a first conductive layer 162and a second conductive layer 164. Device 100 may be fabricated bydepositing the layers described, in order. The properties and functionsof these various layers, as well as example materials, are described inmore detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which areincorporated by reference.

More examples for each of these layers are available. For example, aflexible and transparent substrate-anode combination is disclosed inU.S. Pat. No. 5,844,363, which is incorporated by reference in itsentirety. An example of a p-doped hole transport layer is m-MTDATA dopedwith F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. PatentApplication Publication No. 2003/0230980, which is incorporated byreference in its entirely. Examples of emissive and host materials aredisclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which isincorporated by reference in its entirety. An example of an n-dopedelectron transport layer is BPhen doped with Li at a molar ratio of 1:1,as disclosed in U.S. Patent Application Publication No. 2003/0230980,which is incorporated by reference in its entirety. U.S. Pat. Nos.5,703,436 and 5,707,745, which are incorporated by reference in theirentireties, disclose examples of cathodes including compound cathodeshaving a thin layer of metal such as Mg:Ag with an overlyingtransparent, electrically-conductive, sputter-deposited ITO layer. Thetheory and use of blocking layers is described in more detail in U.S.Pat. No. 6,097,147 and U.S. Patent Application Publication No.2003/0230980, which are incorporated by reference in their entireties.Examples of injection layers are provided in U.S. Patent ApplicationPublication No. 2004/0174116, which is incorporated by reference in itsentirety. A description of protective layers may be found in U.S. PatentApplication Publication No. 2004/0174116, which is incorporated byreference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210,a cathode 215, an emissive layer 220, a hole transport layer 225, and ananode 230. Device 200 may be fabricated by depositing the layersdescribed, in order. Because the most common OLED configuration has acathode disposed over the anode, and device 200 has cathode 215 disposedunder anode 230, device 200 may be referred to as an “inverted” OLED.Materials similar to those described with respect to device 100 may beused in the corresponding layers of device 200. FIG. 2 provides oneexample of how some layers may be omitted from the structure of device100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided byway of non-limiting example, and it is understood that embodiments ofthe invention may be used in connection with a wide variety of otherstructures. The specific materials and structures described areexemplary in nature, and other materials and structures may be used.Functional OLEDs may be achieved by combining the various layersdescribed in different ways, or layers may be omitted entirely, based ondesign, performance, and cost factors. Other layers not specificallydescribed may also be included. Materials other than those specificallydescribed may be used. Although many of the examples provided hereindescribe various layers as comprising a single material, it isunderstood that combinations of materials, such as a mixture of host anddopant, or more generally a mixture, may be used. Also, the layers mayhave various sublayers. The names given to the various layers herein arenot intended to be strictly limiting. For example, in device 200, holetransport layer 225 transports holes and injects holes into emissivelayer 220, and may be described as a hole transport layer or a holeinjection layer. In one embodiment, an OLED may be described as havingan “organic layer” disposed between a cathode and an anode. This organiclayer may comprise a single layer, or may further comprise multiplelayers of different organic materials as described, for example, withrespect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used,such as OLEDs comprised of polymeric materials (PLEDs) such as disclosedin U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated byreference in its entirety. By way of further example, OLEDs having asingle organic layer may be used. OLEDs may be stacked, for example asdescribed in U.S. Pat. No. 5,707,745 to Forrest et al. which isincorporated by reference in its entirety. The OLED structure maydeviate from the simple layered structure illustrated in FIGS. 1 and 2.For example, the substrate may include an angled reflective surface toimprove out-coupling, such as a mesa structure as described in U.S. Pat.No. 6,091,195 to Forrest et al., and/or a pit structure as described inU.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated byreference in their entireties.

Unless otherwise specified, any of the layers of the various embodimentsmay be deposited by any suitable method. For the organic layers,preferred methods include thermal evaporation, ink-jet, such asdescribed in U.S. Pat. Nos. 6,013,982 and 6,087,196, which areincorporated by reference in their entireties, organic vapor phasedeposition (OVPD), such as described in U.S. Pat. No. 6,337,102 toForrest et al., which is incorporated by reference in its entirety, anddeposition by organic vapor jet printing (OVJP), such as described inU.S. Pat. No. 7,431,968, which is incorporated by reference in itsentirety. Other suitable deposition methods include spin coating andother solution based processes. Solution based processes are preferablycarried out in nitrogen or an inert atmosphere. For the other layers,preferred methods include thermal evaporation. Preferred patterningmethods include deposition through a mask, cold welding such asdescribed in U.S. Pat. Nos. 6,294,398 and 6,468,819, which areincorporated by reference in their entireties, and patterning associatedwith some of the deposition methods such as ink-jet and OVJD. Othermethods may also be used. The materials to be deposited may be modifiedto make them compatible with a particular deposition method. Forexample, substituents such as alkyl and aryl groups, branched orunbranched, and preferably containing at least 3 carbons, may be used insmall molecules to enhance their ability to undergo solution processing.Substituents having 20 carbons or more may be used, and 3-20 carbons isa preferred range. Materials with asymmetric structures may have bettersolution processability than those having symmetric structures, becauseasymmetric materials may have a lower tendency to recrystallize.Dendrimer substituents may be used to enhance the ability of smallmolecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the presentinvention may further optionally comprise a barrier layer. One purposeof the barrier layer is to protect the electrodes and organic layersfrom damaging exposure to harmful species in the environment includingmoisture, vapor and/or gases, etc. The barrier layer may be depositedover, under or next to a substrate, an electrode, or over any otherparts of a device including an edge. The barrier layer may comprise asingle layer, or multiple layers. The barrier layer may be formed byvarious known chemical vapor deposition techniques and may includecompositions having a single phase as well as compositions havingmultiple phases. Any suitable material or combination of materials maybe used for the barrier layer. The barrier layer may incorporate aninorganic or an organic compound or both. The preferred barrier layercomprises a mixture of a polymeric material and a non-polymeric materialas described in U.S. Pat. No. 7,968,146. PCT Pat. Application Nos.PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporatedby reference in their entireties. To be considered a “mixture”, theaforesaid polymeric and non-polymeric materials comprising the barrierlayer should be deposited under the same reaction conditions and/or atthe same time. The weight ratio of polymeric to non-polymeric materialmay be in the range of 95:5 to 5:95. The polymeric material and thenon-polymeric material may be created from the same precursor material.In one example, the mixture of a polymeric material and a non-polymericmaterial consists essentially of polymeric silicon and inorganicsilicon.

Devices fabricated in accordance with embodiments of the invention canbe incorporated into a wide variety of electronic component modules (orunits) that can be incorporated into a variety of electronic products orintermediate components. Examples of such electronic products orintermediate components include display screens, lighting devices suchas discrete light source devices or lighting panels, etc. that can beutilized by the end-user product manufacturers. Such electroniccomponent modules can optionally include the driving electronics and/orpower source(s). Devices fabricated in accordance with embodiments ofthe invention can be incorporated into a wide variety of consumerproducts that have one or more of the electronic component modules (orunits) incorporated therein. Such consumer products would include anykind of products that include one or more light source(s) and/or one ormore of some type of visual displays. Some examples of such consumerproducts include flat panel displays, computer monitors, medicalmonitors, televisions, billboards, lights for interior or exteriorillumination and/or signaling, heads-up displays, fully or partiallytransparent displays, flexible displays, laser printers, telephones,cell phones, tablets, phablets, personal digital assistants (PDAs),wearable device, laptop computers, digital cameras, camcorders,viewfinders, micro-displays, 3-D displays, vehicles, a large area wall,theater or stadium screen, or a sign. Various control mechanisms may beused to control devices fabricated in accordance with the presentinvention, including passive matrix and active matrix. Many of thedevices are intended for use in a temperature range comfortable tohumans, such as 18 degrees C. to 30 degrees C., and more preferably atroom temperature (20-25 degrees C.), but could be used outside thistemperature range, for example, from −40 degree C. to +80 degree C.

The materials and structures described herein may have applications indevices other than OLEDs. For example, other optoelectronic devices suchas organic solar cells and organic photodetectors may employ thematerials and structures. More generally, organic devices, such asorganic transistors, may employ the materials and structures.

The term “halo,” “halogen,” or “halide” as used herein includesfluorine, chlorine, bromine, and iodine.

The term “alkyl” as used herein contemplates both straight and branchedchain alkyl radicals. Preferred alkyl groups are those containing fromone to fifteen carbon atoms and includes methyl, ethyl, propyl,1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl,1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, thealkyl group may be optionally substituted.

The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals.Preferred cycloalkyl groups are those containing 3 to 10 ring carbonatoms and includes cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, andthe like. Additionally, the cycloalkyl group may be optionallysubstituted.

The term “alkenyl” as used herein contemplates both straight andbranched chain alkene radicals. Preferred alkenyl groups are thosecontaining two to fifteen carbon atoms. Additionally, the alkenyl groupmay be optionally substituted.

The term “alkynyl” as used herein contemplates both straight andbranched chain alkyne radicals. Preferred alkynyl groups are thosecontaining two to fifteen carbon atoms. Additionally, the alkynyl groupmay be optionally substituted.

The terms “aralkyl” or “arylalkyl” as used herein are usedinterchangeably and contemplate an alkyl group that has as a substituentan aromatic group. Additionally, the aralkyl group may be optionallysubstituted.

The term “heterocyclic group” as used herein contemplates aromatic andnon-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also meansheteroaryl. Preferred hetero-non-aromatic cyclic groups are thosecontaining 3 or 7 ring atoms which includes at least one hetero atom,and includes cyclic amines such as morpholino, piperdino, pyrrolidino,and the like, and cyclic ethers, such as tetrahydrofuran,tetrahydropyran, and the like. Additionally, the heterocyclic group maybe optionally substituted.

The term “aryl” or “aromatic group” as used herein contemplatessingle-ring groups and polycyclic ring systems. The polycyclic rings mayhave two or more rings in which two carbons are common to two adjoiningrings (the rings are “fused”) wherein at least one of the rings isaromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl,heterocycles, and/or heteroaryls. Preferred aryl groups are thosecontaining six to thirty carbon atoms, preferably six to twenty carbonatoms, more preferably six to twelve carbon atoms. Especially preferredis an aryl group having six carbons, ten carbons or twelve carbons.Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene,tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene,fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl,biphenyl, triphenyl, triphenylene, fluorene, and naphthalene.Additionally, the aryl group may be optionally substituted.

The term “heteroaryl” as used herein contemplates single-ringhetero-aromatic groups that may include from one to five heteroatoms.The term heteroaryl also includes polycyclic hetero-aromatic systemshaving two or more rings in which two atoms are common to two adjoiningrings (the rings are “fused”) wherein at least one of the rings is aheteroaryl. e.g., the other rings can be cycloalkyls, cycloalkenyls,aryl, heterocycles, and/or heteroaryls. Preferred heteroaryl groups arethose containing three to thirty carbon atoms, preferably three totwenty carbon atoms, more preferably three to twelve carbon atoms.Suitable heteroaryl groups include dibenzothiophene, dibenzofuran,dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene,benzoselenophene, carbazole, indolocarbazole, pyridylindole,pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole,oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine,pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine,indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole,benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline,quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine,phenazine, phenothiazine, phenoxazine, benzofuropyridine,furodipyridine, benzothienopyridine, thienodipyridine,benzoselenophenopyridine, and selenophenodipyridine, preferablydibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole,indolocarbazole, imidazole, pyridine, triazine, benzimidazole, andaza-analogs thereof. Additionally, the heteroaryl group may beoptionally substituted.

The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group,aryl, and heteroaryl may be unsubstituted or may be substituted with oneor more substituents selected from the group consisting of deuterium,halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether,ester, nitrile, isonitrile, sulfanyl, sulfonyl, sulfonyl, phosphino, andcombinations thereof.

As used herein, “substituted” indicates that a substituent other than His bonded to the relevant position, such as carbon. Thus, for example,where R¹ is mono-substituted, then one R¹ must be other than H.Similarly, where R¹ is di-substituted, then two of R¹ must be other thanH. Similarly, where R¹ is unsubstituted. R¹ is hydrogen for allavailable positions.

The “aza” designation in the fragments described herein, i.e.aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more ofthe C—H groups in the respective fragment can be replaced by a nitrogenatom, for example, and without any limitation, azatriphenyleneencompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Oneof ordinary skill in the art can readily envision other nitrogen analogsof the aza-derivatives described above, and all such analogs areintended to be encompassed by the terms as set forth herein.

It is to be understood that when a molecular fragment is described asbeing a substituent or otherwise attached to another moiety, its namemay be written as if it were a fragment (e.g. phenyl, phenylene,naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g.benzene, naphthalene, dibenzofuran). As used herein, these differentways of designating a substituent or attached fragment are considered tobe equivalent.

According to an aspect of the present disclosure, ligands containingfive-membered ring fused on pyridine or pyrimidine ring combined withpartially fluorinated side chains that are found to be useful asphosphorescent light-emitting metal complexes for organic light emittingdevices are disclosed. The resulting light-emitting metal complexesexhibited improved external quantum efficiency and lifetimes.

Some exemplary ligands disclosed herein are fluoropyrimidine,thienopyrimidine, pyrrolopyrimidine, and cyclopentapyrimidine. In someembodiments, these ligands can be combined with aliphatic substituentscontaining at least one F atom. The combination of these two moieties ona single ligand was used for multiple reasons. Pyridine- orpyrimidine-based ligands used for red dopants have shown very gooddevice efficiency and good lifetime. The incorporation of one ormultiple side chains containing F atom will allow fine tuning of thecolor and especially provide a red shift.

According to some embodiments, a compound comprising a ligand L_(A) ofFormula I,

is disclosed; wherein ring A is a 5-membered or 6-membered carbocyclicor heterocyclic ring:

wherein R is fused to ring B and has a structure of Formula II,

wherein the wave lines indicate bonds to ring B;

wherein R¹ represents mono, di, tri, or tetra substitution, or nosubstitution;

wherein R² represents mono or di substitution, or no substitution;

wherein X¹, X², X³, and X⁴ are each independently carbon or nitrogen;

wherein at least two adjacent of X¹, X², X³, and X⁴ are carbon and fuseto R;

wherein X is selected from the group consisting of BR′, NR′, PR′, O, S,Sc, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″;

wherein R¹, R², R³, R⁴, R′, and R″ are each independently selected fromthe group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof; and wherein any twoadjacent substituents are optionally joined to form into a ring;

wherein at least one of R¹ and R⁴ comprises a chemical group selectedfrom the group consisting of alkyl, cycloalkyl, partially fluorinatedalkyl, partially fluorinated cycloalkyl, and combinations thereof;

wherein the ligand L_(A) is coordinated to a metal M;

wherein the ligand L_(A) is optionally linked with other ligands tocomprise a tridentate, tetradentate, pentadentate, or hexadentateligand, and wherein M is optionally coordinated to other ligands.

In some embodiments of the compound, M is selected from the groupconsisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu.

In some embodiments of the compound, M is Ir or Pt.

In some embodiments of the compound, the ligand L_(A) is selected fromthe group consisting of:

In some embodiments of the compound, the ligand L_(A) is:

In some embodiments of the compound, the ligand L_(A) is:

In some embodiments of the compound, at least one of R³ and R⁴ is achemical group selected from the group consisting of alkyl, cycloalkyl,partially fluorinated alkyl, partially fluorinated cycloalkyl, andcombinations thereof.

In some embodiments of the compound, at least one of R³ and R⁴ is achemical group selected from the group consisting of partiallyfluorinated alkyl, partially fluorinated cycloalkyl, and combinationsthereof.

In some embodiments of the compound, R³ and R⁴ are not hydrogen.

In some embodiments of the compound, at least one of X¹, X², X³, and X⁴is nitrogen.

In some embodiments of the compound, X is O.

In some embodiments of the compound, X is NR′.

In some embodiments of the compound, X is CR′R″ or SiR′R″.

In some embodiments of the compound. R¹, R², R³, R⁴, R′ and R″ are eachindependently selected from the group consisting of hydrogen, deuterium,alkyl, cycloalkyl, and combinations thereof.

In some embodiments of the compound, R¹, R², R³, R⁴, R′ and R″ are eachindependently selected from the group consisting of hydrogen, deuterium,methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl,cyclohexyl, and combinations thereof.

In some embodiments of the compound, at least one of R³ and R⁴ isselected from the group consisting of:

In some embodiments of the compound, R³ and R⁴ are joined to form a ringstructure selected from the group consisting of:

In some embodiments of the compound, at least one of R³ and R⁴ isselected from the group consisting of:

In some embodiments of the compound, the ligand L_(A) is selected fromthe group consisting of:

wherein R¹, R², R³, and R′ are as defined above.

In some embodiments of the compound, the ligand L_(A) is selected fromthe group consisting of L_(A1) through L_(A750) defined as follows:

L_(A1) through L_(A375) are based on a structure of Formula IV,

in which R³, R⁴, and X are defined as shown in Table 1 below:

TABLE 1 Ligand R³ R⁴ X L_(A1) H R^(A2) O L_(A2) R^(A2) R^(A2) O L_(A3)R^(A3) R^(A2) O L_(A4) R^(A14) R^(A2) O L_(A5) R^(A22) R^(A2) O L_(A6)R^(A28) R^(A2) O L_(A7) H R^(A3) O L_(A8) R^(A2) R^(A3) O L_(A9) R^(A3)R^(A3) O L_(A10) R^(A14) R^(A3) O L_(A11) R^(A22) R^(A3) O L_(A12)R^(A28) R^(A3) O L_(A13) H R^(A14) O L_(A14) R^(A2) R^(A14) O L_(A15)R^(A3) R^(A14) O L_(A16) R^(A14) R^(A14) O L_(A17) R^(A22) R^(A14) OL_(A18) R^(A28) R^(A14) O L_(A19) H R^(A22) O L_(A20) R^(A2) R^(A22) OL_(A21) R^(A3) R^(A22) O L_(A22) R^(A14) R^(A22) O L_(A23) R^(A22)R^(A22) O L_(A24) R^(A28) R^(A22) O L_(A25) H R^(A28) O L_(A26) R^(A2)R^(A28) O L_(A27) R^(A3) R^(A28) O L_(A28) R^(A14) R^(A28) O L_(A29)R^(A22) R^(A28) O L_(A30) R^(A28) R^(A28) O L_(A31) R^(A2) H O L_(A32)R^(A3) H O L_(A33) R^(A14) H O L_(A34) R^(A22) H O L_(A35) R^(A28) H OL_(A36) R^(A2) R^(B1) O L_(A37) R^(A3) R^(B1) O L_(A38) R^(A14) R^(B1) OL_(A39) R^(A12) R^(B1) O L_(A40) R^(A28) R^(B1) O L_(A41) R^(A2) R^(B2)O L_(A42) R^(A3) R^(B2) O L_(A43) R^(A14) R^(B2) O L_(A44) R^(A22)R^(B2) O L_(A45) R^(A28) R^(B2) O L_(A46) R^(A2) R^(B3) O L_(A47) R^(A3)R^(B3) O L_(A48) R^(A14) R^(B3) O L_(A49) R^(A22) R^(B3) O L_(A50)R^(A28) R^(B3) O L_(A51) R^(A2) R^(B4) O L_(A52) R^(A3) R^(B4) O L_(A53)R^(A14) R^(B4) O L_(A54) R^(A22) R^(B4) O L_(A55) R^(A28) R^(B4) OL_(A56) R^(B1) R^(A2) O L_(A57) R^(B1) R^(A3) O L_(A58) R^(B1) R^(A14) OL_(A59) R^(B1) R^(A22) O L_(A60) R^(B1) R^(A28) O L_(A61) R^(B2) R^(A2)O L_(A62) R^(B2) R^(A3) O L_(A63) R^(B2) R^(A14) O L_(A64) R^(B2)R^(A22) O L_(A65) R^(B2) R^(A28) O L_(A66) R^(B3) R^(A2) O L_(A67)R^(B3) R^(A3) O L_(A68) R^(B3) R^(A14) O L_(A69) R^(B3) R^(A22) OL_(A70) R^(B3) R^(A28) O L_(A71) R^(B4) R^(A2) O L_(A72) R^(B4) R^(A3) OL_(A73) R^(B4) R^(A14) O L_(A74) R^(B4) R^(A22) O L_(A75) R^(B4) R^(A28)O L_(A76) H R^(A2) S L_(A77) R^(A2) R^(A2) S L_(A78) R^(A3) R^(A2) SL_(A79) R^(A14) R^(A2) S L_(A80) R^(A22) R^(A2) S L_(A81) R^(A28) R^(A2)S L_(A82) H R^(A3) S L_(A83) R^(A2) R^(A3) S L_(A84) R^(A3) R^(A3) SL_(A85) R^(A14) R^(A3) S L_(A86) R^(A22) R^(A3) S L_(A87) R^(A28) R^(A3)S L_(A88) H R^(A14) S L_(A89) R^(A2) R^(A14) S L_(A90) R^(A3) R^(A14) SL_(A91) R^(A14) R^(A14) S L_(A92) R^(A22) R^(A14) S L_(A93) R^(A28)R^(A14) S L_(A94) H R^(A22) S L_(A95) R^(A2) R^(A22) S L_(A96) R^(A3)R^(A22) S L_(A97) R^(A14) R^(A22) S L_(A98) R^(A22) R^(A22) S L_(A99)R^(A28) R^(A22) S L_(A100) H R^(A28) S L_(A101) R^(A2) R^(A28) SL_(A102) R^(A3) R^(A28) S L_(A103) R^(A14) R^(A28) S L_(A104) R^(A22)R^(A28) S L_(A105) R^(A28) R^(A28) S L_(A106) R^(A2) H S L_(A107) R^(A3)H S L_(A108) R^(A14) H S L_(A109) R^(A22) H S L_(A110) R^(A28) H SL_(A111) R^(A2) R^(B1) S L_(A112) R^(A3) R^(B1) S L_(A113) R^(A14)R^(B1) S L_(A114) R^(A22) R^(B1) S L_(A115) R^(A28) R^(B1) S L_(A116)R^(A2) R^(B2) S L_(A117) R^(A3) R^(B2) S L_(A118) R^(A14) R^(B2) SL_(A119) R^(A22) R^(B2) S L_(A120) R^(A28) R^(B2) S L_(A121) R^(A2)R^(B3) S L_(A122) R^(A3) R^(B3) S L_(A123) R^(A14) R^(B3) S L_(A124)R^(A22) R^(B3) S L_(A125) R^(A28) R^(B3) S L_(A126) R^(A2) R^(B4) SL_(A127) R^(A3) R^(B4) S L_(A128) R^(A14) R^(B4) S L_(A129) R^(A22)R^(B4) S L_(A130) R^(A28) R^(B4) S L_(A131) R^(B1) R^(A2) S L_(A132)R^(B1) R^(A3) S L_(A133) R^(B1) R^(A14) S L_(A134) R^(B1) R^(A22) SL_(A135) R^(B1) R^(A28) S L_(A136) R^(B2) R^(A2) S L_(A137) R^(B2)R^(A3) S L_(A138) R^(B2) R^(A14) S L_(A139) R^(B2) R^(A22) S L_(A140)R^(B2) R^(A28) S L_(A141) R^(B3) R^(A2) S L_(A142) R^(B3) R^(A3) SL_(A143) R^(B3) R^(A14) S L_(A144) R^(B3) R^(A22) S L_(A145) R^(B3)R^(A28) S L_(A146) R^(B4) R^(A2) S L_(A147) R^(B4) R^(A3) S L_(A148)R^(B4) R^(A14) S L_(A149) R^(B4) R^(A22) S L_(A150) R^(B4) R^(A28) SL_(A151) H R^(A2) C(CH₃)₂ L_(A152) R^(A2) R^(A2) C(CH₃)₂ L_(A153) R^(A3)R^(A2) C(CH₃)₂ L_(A154) R^(A14) R^(A2) C(CH₃)₂ L_(A155) R^(A22) R^(A2)C(CH₃)₂ L_(A156) R^(A28) R^(A2) C(CH₃)₂ L_(A157) H R^(A3) C(CH₃)₂L_(A158) R^(A2) R^(A3) C(CH₃)₂ L_(A159) R^(A3) R^(A3) C(CH₃)₂ L_(A160)R^(A14) R^(A3) C(CH₃)₂ L_(A161) R^(A22) R^(A3) C(CH₃)₂ L_(A162) R^(A28)R^(A3) C(CH₃)₂ L_(A163) H R^(A14) C(CH₃)₂ L_(A164) R^(A2) R^(A14)C(CH₃)₂ L_(A165) R^(A3) R^(A14) C(CH₃)₂ L_(A166) R^(A14) R^(A14) C(CH₃)₂L_(A167) R^(A22) R^(A14) C(CH₃)₂ L_(A168) R^(A28) R^(A14) C(CH₃)₂L_(A169) H R^(A22) C(CH₃)₂ L_(A170) R^(A2) R^(A22) C(CH₃)₂ L_(A171)R^(A3) R^(A22) C(CH₃)₂ L_(A172) R^(A14) R^(A22) C(CH₃)₂ L_(A173) R^(A22)R^(A22) C(CH₃)₂ L_(A174) R^(A28) R^(A22) C(CH₃)₂ L_(A175) H R^(A28)C(CH₃)₂ L_(A176) R^(A2) R^(A28) C(CH₃)₂ L_(A177) R^(A3) R^(A28) C(CH₃)₂L_(A178) R^(A14) R^(A28) C(CH₃)₂ L_(A179) R^(A22) R^(A28) C(CH₃)₂L_(A180) R^(A28) R^(A28) C(CH₃)₂ L_(A181) R^(A2) H C(CH₃)₂ L_(A182)R^(A3) H C(CH₃)₂ L_(A183) R^(A14) H C(CH₃)₂ L_(A184) R^(A22) H C(CH₃)₂L_(A185) R^(A28) H C(CH₃)₂ L_(A186) R^(A2) R^(B1) C(CH₃)₂ L_(A187)R^(A3) R^(B1) C(CH₃)₂ L_(A188) R^(A14) R^(B1) C(CH₃)₂ L_(A189) R^(A22)R^(B1) C(CH₃)₂ L_(A190) R^(A28) R^(B1) C(CH₃)₂ L_(A191) R^(A2) R^(B2)C(CH₃)₂ L_(A192) R^(A3) R^(B2) C(CH₃)₂ L_(A193) R^(A14) R^(B2) C(CH₃)₂L_(A194) R^(A22) R^(B2) C(CH₃)₂ L_(A195) R^(A28) R^(B2) C(CH₃)₂ L_(A196)R^(A2) R^(B3) C(CH₃)₂ L_(A197) R^(A3) R^(B3) C(CH₃)₂ L_(A198) R^(A14)R^(B3) C(CH₃)₂ L_(A199) R^(A22) R^(B3) C(CH₃)₂ L_(A200) R^(A28) R^(B3)C(CH₃)₂ L_(A201) R^(A2) R^(B4) C(CH₃)₂ L_(A202) R^(A3) R^(B4) C(CH₃)₂L_(A203) R^(A14) R^(B4) C(CH₃)₂ L_(A204) R^(A22) R^(B4) C(CH₃)₂ L_(A205)R^(A28) R^(B4) C(CH₃)₂ L_(A206) R^(B1) R^(A2) C(CH₃)₂ L_(A207) R^(B1)R^(A3) C(CH₃)₂ L_(A208) R^(B1) R^(A14) C(CH₃)₂ L_(A209) R^(B1) R^(A22)C(CH₃)₂ L_(A210) R^(B1) R^(A28) C(CH₃)₂ L_(A211) R^(B2) R^(A2) C(CH₃)₂L_(A212) R^(B2) R^(A3) C(CH₃)₂ L_(A213) R^(B2) R^(A14) C(CH₃)₂ L_(A214)R^(B2) R^(A22) C(CH₃)₂ L_(A215) R^(B2) R^(A28) C(CH₃)₂ L_(A216) R^(B3)R^(A2) C(CH₃)₂ L_(A217) R^(B3) R^(A3) C(CH₃)₂ L_(A218) R^(B3) R^(A14)C(CH₃)₂ L_(A219) R^(B3) R^(A22) C(CH₃)₂ L_(A220) R^(B3) R^(A28) C(CH₃)₂L_(A221) R^(B4) R^(A2) C(CH₃)₂ L_(A222) R^(B4) R^(A3) C(CH₃)₂ L_(A223)R^(B4) R^(A14) C(CH₃)₂ L_(A224) R^(B4) R^(A22) C(CH₃)₂ L_(A225) R^(B4)R^(A28) C(CH₃)₂ L_(A226) H R^(A2) NCH₃ L_(A227) R^(A2) R^(A2) NCH₃L_(A228) R^(A3) R^(A2) NCH₃ L_(A229) R^(A14) R^(A2) NCH₃ L_(A230)R^(A22) R^(A2) NCH₃ L_(A231) R^(A28) R^(A2) NCH₃ L_(A232) H R^(A3) NCH₃L_(A233) R^(A2) R^(A3) NCH₃ L_(A234) R^(A3) R^(A3) NCH₃ L_(A235) R^(A14)R^(A3) NCH₃ L_(A236) R^(A22) R^(A3) NCH₃ L_(A237) R^(A28) R^(A3) NCH₃L_(A238) H R^(A14) NCH₃ L_(A239) R^(A2) R^(A14) NCH₃ L_(A240) R^(A3)R^(A14) NCH₃ L_(A241) R^(A14) R^(A14) NCH₃ L_(A242) R^(A22) R^(A14) NCH₃L_(A243) R^(A28) R^(A14) NCH₃ L_(A244) H R^(A22) NCH₃ L_(A245) R^(A2)R^(A22) NCH₃ L_(A246) R^(A3) R^(A22) NCH₃ L_(A247) R^(A14) R^(A22) NCH₃L_(A248) R^(A22) R^(A22) NCH₃ L_(A249) R^(A28) R^(A22) NCH₃ L_(A250) HR^(A28) NCH₃ L_(A251) R^(A2) R^(A28) NCH₃ L_(A252) R^(A3) R^(A28) NCH₃L_(A253) R^(A14) R^(A28) NCH₃ L_(A254) R^(A22) R^(A28) NCH₃ L_(A255)R^(A28) R^(A28) NCH₃ L_(A256) R^(A2) H NCH₃ L_(A257) R^(A3) H NCH₃L_(A258) R^(A14) H NCH₃ L_(A259) R^(A22) H NCH₃ L_(A260) R^(A28) H NCH₃L_(A261) R^(A2) R^(B1) NCH₃ L_(A262) R^(A3) R^(B1) NCH₃ L_(A263) R^(A14)R^(B1) NCH₃ L_(A264) R^(A22) R^(BI) NCH₃ L_(A265) R^(A28) R^(B1) NCH₃L_(A266) R^(A2) R^(B2) NCH₃ L_(A267) R^(A3) R^(B2) NCH₃ L_(A268) R^(A14)R^(B2) NCH₃ L_(A269) R^(A22) R^(B2) NCH₃ L_(A270) R^(A28) R^(B2) NCH₃L_(A271) R^(A2) R^(B3) NCH₃ L_(A272) R^(A3) R^(B3) NCH₃ L_(A273) R^(A14)R^(B3) NCH₃ L_(A274) R^(A22) R^(B3) NCH₃ L_(A275) R^(A28) R^(B3) NCH₃L_(A276) R^(A2) R^(B4) NCH₃ L_(A277) R^(A3) R^(B4) NCH₃ L_(A278) R^(A14)R^(B4) NCH₃ L_(A279) R^(A22) R^(B4) NCH₃ L_(A280) R^(A28) R^(B4) NCH₃L_(A281) R^(A2) R^(B1) NCH₃ L_(A282) R^(A3) R^(B1) NCH₃ L_(A283) R^(A14)R^(B1) NCH₃ L_(A284) R^(A22) R^(B1) NCH₃ L_(A285) R^(A28) R^(B1) NCH₃L_(A286) R^(A2) R^(B2) NCH₃ L_(A287) R^(A3) R^(B2) NCH₃ L_(A288) R^(A14)R^(B2) NCH₃ L_(A289) R^(A22) R^(B2) NCH₃ L_(A290) R^(A28) R^(B2) NCH₃L_(A291) R^(A2) R^(B3) NCH₃ L_(A292) R^(A3) R^(B3) NCH₃ L_(A293) R^(A14)R^(B3) NCH₃ L_(A294) R^(A22) R^(B3) NCH₃ L_(A295) R^(A28) R^(B3) NCH₃L_(A296) R^(A2) R^(B4) NCH₃ L_(A297) R^(A3) R^(B4) NCH₃ L_(A298) R^(A14)R^(B4) NCH₃ L_(A299) R^(A22) R^(B4) NCH₃ L_(A300) R^(A28) R^(B4) NCH₃L_(A301) H R^(A2) N(isobutyl) L_(A302) R^(A2) R^(A2) N(isobutyl)L_(A303) R^(A3) R^(A2) N(isobutyl) L_(A304) R^(A14) R^(A2) N(isobutyl)L_(A305) R^(A22) R^(A2) N(isobutyl) L_(A306) R^(A28) R^(A2) N(isobutyl)L_(A307) H R^(A3) N(isobutyl) L_(A308) R^(A2) R^(A3) N(isobutyl)L_(A309) R^(A3) R^(A3) N(isobutyl) L_(A310) R^(A14) R^(A3) N(isobutyl)L_(A311) R^(A22) R^(A3) N(isobutyl) L_(A312) R^(A28) R^(A3) N(isobutyl)L_(A313) H R^(A14) N(isobutyl) L_(A314) R^(A2) R^(A14) N(isobutyl)L_(A315) R^(A3) R^(A14) N(isobutyl) L_(A316) R^(A14) R^(A14) N(isobutyl)L_(A317) R^(A22) R^(A14) N(isobutyl) L_(A318) R^(A28) R^(A14)N(isobutyl) L_(A319) H R^(A22) N(isobutyl) L_(A320) R^(A2) R^(A22)N(isobutyl) L_(A321) R^(A3) R^(A22) N(isobutyl) L_(A322) R^(A14) R^(A22)N(isobutyl) L_(A323) R^(A22) R^(A22) N(isobutyl) L_(A324) R^(A28)R^(A22) N(isobutyl) L_(A325) H R^(A28) N(isobutyl) L_(A326) R^(A2)R^(A28) N(isobutyl) L_(A327) R^(A3) R^(A28) N(isobutyl) L_(A328) R^(A14)R^(A28) N(isobutyl) L_(A329) R^(A22) R^(A28) N(isobutyl) L_(A330)R^(A28) R^(A28) N(isobutyl) L_(A331) R^(A2) H N(isobutyl) L_(A332)R^(A3) H N(isobutyl) L_(A333) R^(A14) H N(isobutyl) L_(A334) R^(A22) HN(isobutyl) L_(A335) R^(A28) H N(isobutyl) L_(A336) R^(A2) R^(B1)N(isobutyl) L_(A337) R^(A3) R^(B1) N(isobutyl) L_(A338) R^(A14) R^(B1)N(isobutyl) L_(A339) R^(A22) R^(B1) N(isobutyl) L_(A340) R^(A28) R^(B1)N(isobutyl) L_(A341) R^(A2) R^(B2) N(isobutyl) L_(A342) R^(A3) R^(B2)N(isobutyl) L_(A343) R^(A14) R^(B2) N(isobutyl) L_(A344) R^(A22) R^(B2)N(isobutyl) L_(A345) R^(A28) R^(B2) N(isobutyl) L_(A346) R^(A2) R^(B3)N(isobutyl) L_(A347) R^(A3) R^(B3) N(isobutyl) L_(A348) R^(A14) R^(B3)N(isobutyl) L_(A349) R^(A22) R^(B3) N(isobutyl) L_(A350) R^(A28) R^(B3)N(isobutyl) L_(A351) R^(A2) R^(B4) N(isobutyl) L_(A352) R^(A3) R^(B4)N(isobutyl) L_(A353) R^(A14) R^(B4) N(isobutyl) L_(A354) R^(A22) R^(B4)N(isobutyl) L_(A355) R^(A28) R^(B4) N(isobutyl) L_(A356) R^(B1) R^(A2)N(isobutyl) L_(A357) R^(B1) R^(A3) N(isobutyl) L_(A358) R^(B1) R^(A14)N(isobutyl) L_(A359) R^(B1) R^(A22) N(isobutyl) L_(A360) R^(B1) R^(A28)N(isobutyl) L_(A361) R^(B2) R^(A2) N(isobutyl) L_(A362) R^(B2) R^(A3)N(isobutyl) L_(A363) R^(B2) R^(A14) N(isobutyl) L_(A364) R^(B2) R^(A22)N(isobutyl) L_(A365) R^(B2) R^(A28) N(isobutyl) L_(A366) R^(B3) R^(A2)N(isobutyl) L_(A367) R^(B3) R^(A3) N(isobutyl) L_(A368) R^(B3) R^(A14)N(isobutyl) L_(A369) R^(B3) R^(A22) N(isobutyl) L_(A370) R^(B3) R^(A28)N(isobutyl) L_(A371) R^(B4) R^(A2) N(isobutyl) L_(A372) R^(B4) R^(A3)N(isobutyl) L_(A373) R^(B4) R^(A14) N(isobutyl) L_(A374) R^(B4) R^(A22)N(isobutyl) L_(A375) R^(B4) R^(A28) N(isobutyl)and L_(A376) through L_(A750) are based on a structure of, Formula V,

in which R³, R⁴, and X are defined as shown in Table 2 below:

TABLE 2 Ligand R³ R⁴ X L_(A376) H R^(A2) O L_(A377) R^(A2) R^(A2) OL_(A378) R^(A3) R^(A2) O L_(A379) R^(A14) R^(A2) O L_(A380) R^(A22)R^(A2) O L_(A381) R^(A28) R^(A2) O L_(A382) H R^(A3) O L_(A383) R^(A2)R^(A3) O L_(A384) R^(A3) R^(A3) O L_(A385) R^(A14) R^(A3) O L_(A386)R^(A22) R^(A3) O L_(A387) R^(A28) R^(A3) O L_(A388) H R^(A14) O L_(A389)R^(A2) R^(A14) O L_(A390) R^(A3) R^(A14) O L_(A391) R^(A14) R^(A14) OL_(A392) R^(A22) R^(A14) O L_(A393) R^(A28) R^(A14) O L_(A394) H R^(A22)O L_(A395) R^(A2) R^(A22) O L_(A396) R^(A3) R^(A22) O L_(A397) R^(A14)R^(A22) O L_(A398) R^(A22) R^(A22) O L_(A399) R^(A28) R^(A22) O L_(A400)H R^(A28) O L_(A401) R^(A2) R^(A28) O L_(A402) R^(A3) R^(A28) O L_(A403)R^(A14) R^(A28) O L_(A404) R^(A22) R^(A28) O L_(A405) R^(A28) R^(A28) OL_(A406) R^(A2) H O L_(A407) R^(A3) H O L_(A408) R^(A14) H O L_(A409)R^(A22) H O L_(A410) R^(A28) H O L_(A411) R^(A2) R^(B1) O L_(A412)R^(A3) R^(B1) O L_(A413) R^(A14) R^(B1) O L_(A414) R^(A22) R^(B1) OL_(A415) R^(A28) R^(B1) O L_(A416) R^(A2) R^(B2) O L_(A417) R^(A3)R^(B2) O L_(A418) R^(A14) R^(B2) O L_(A419) R^(A22) R^(B2) O L_(A420)R^(A28) R^(B2) O L_(A421) R^(A2) R^(B3) O L_(A422) R^(A3) R^(B3) OL_(A423) R^(A14) R^(B3) O L_(A424) R^(A22) R^(B3) O L_(A425) R^(A28)R^(B3) O L_(A426) R^(A2) R^(B4) O L_(A427) R^(A3) R^(B4) O L_(A428)R^(A14) R^(B4) O L_(A429) R^(A22) R^(B4) O L_(A430) R^(A28) R^(B4) OL_(A431) R^(B1) R^(A2) O L_(A432) R^(B1) R^(A3) O L_(A433) R^(B1)R^(A14) O L_(A434) R^(B1) R^(A22) O L_(A435) R^(B1) R^(A28) O L_(A436)R^(B2) R^(A2) O L_(A437) R^(B2) R^(A3) O L_(A438) R^(B2) R^(A14) OL_(A439) R^(B2) R^(A22) O L_(A440) R^(B2) R^(A28) O L_(A441) R^(B3)R^(A2) O L_(A442) R^(B3) R^(A3) O L_(A443) R^(B3) R^(A14) O L_(A444)R^(B3) R^(A22) O L_(A445) R^(B3) R^(A28) O L_(A446) R^(B4) R^(A2) OL_(A447) R^(B4) R^(A3) O L_(A448) R^(B4) R^(A14) O L_(A449) R^(B4)R^(A22) O L_(A450) R^(B4) R^(A28) O L_(A451) H R^(A2) S L_(A452) R^(A2)R^(A2) S L_(A453) R^(A3) R^(A2) S L_(A454) R^(A14) R^(A2) S L_(A455)R^(A22) R^(A2) S L_(A456) R^(A28) R^(A2) S L_(A457) H R^(A3) S L_(A458)R^(A2) R^(A3) S L_(A459) R^(A3) R^(A3) S L_(A460) R^(A14) R^(A3) SL_(A461) R^(A22) R^(A3) S L_(A462) R^(A28) R^(A3) S L_(A463) H R^(A14) SL_(A464) R^(A2) R^(A14) S L_(A465) R^(A3) R^(A14) S L_(A466) R^(A14)R^(A14) S L_(A467) R^(A22) R^(A14) S L_(A468) R^(A28) R^(A14) S L_(A469)H R^(A22) S L_(A470) R^(A2) R^(A22) S L_(A471) R^(A3) R^(A22) S L_(A472)R^(A14) R^(A22) S L_(A473) R^(A22) R^(A22) S L_(A474) R^(A28) R^(A22) SL_(A475) H R^(A28) S L_(A476) R^(A2) R^(A28) S L_(A477) R^(A3) R^(A28) SL_(A478) R^(A14) R^(A28) S L_(A479) R^(A22) R^(A28) S L_(A480) R^(A28)R^(A28) S L_(A481) R^(A2) H S L_(A482) R^(A3) H S L_(A483) R^(A14) H SL_(A484) R^(A22) H S L_(A485) R^(A28) H S L_(A486) R^(A2) R^(B1) SL_(A487) R^(A3) R^(B1) S L_(A488) R^(A14) R^(B1) S L_(A489) R^(A22)R^(B1) S L_(A490) R^(A28) R^(B1) S L_(A491) R^(A2) R^(B2) S L_(A492)R^(A3) R^(B2) S L_(A493) R^(A14) R^(B2) S L_(A494) R^(A22) R^(B2) SL_(A495) R^(A28) R^(B2) S L_(A496) R^(A2) R^(B3) S L_(A497) R^(A3)R^(B3) S L_(A498) R^(A14) R^(B3) S L_(A499) R^(A22) R^(B3) S L_(A500)R^(A28) R^(B3) S L_(A501) R^(A2) R^(B4) S L_(A502) R^(A3) R^(B4) SL_(A503) R^(A14) R^(B4) S L_(A504) R^(A22) R^(B4) S L_(A505) R^(A28)R^(B4) S L_(A506) R^(B1) R^(A2) S L_(A507) R^(B1) R^(A3) S L_(A508)R^(B1) R^(A14) S L_(A509) R^(B1) R^(A22) S L_(A510) R^(B1) R^(A28) SL_(A511) R^(B2) R^(A2) S L_(A512) R^(B2) R^(A3) S L_(A513) R^(B2)R^(A14) S L_(A514) R^(B2) R^(A22) S L_(A515) R^(B2) R^(A28) S L_(A516)R^(B3) R^(A2) S L_(A517) R^(B3) R^(A3) S L_(A518) R^(B3) R^(A14) SL_(A519) R^(B3) R^(A22) S L_(A520) R^(B3) R^(A28) S L_(A521) R^(B4)R^(A2) S L_(A522) R^(B4) R^(A3) S L_(A523) R^(B4) R^(A14) S L_(A524)R^(B4) R^(A22) S L_(A525) R^(B4) R^(A28) S L_(A526) H R^(A2) C(CH₃)₂L_(A527) R^(A2) R^(A2) C(CH₃)₂ L_(A528) R^(A3) R^(A2) C(CH₃)₂ L_(A529)R^(A14) R^(A2) C(CH₃)₂ L_(A530) R^(A22) R^(A2) C(CH₃)₂ L_(A531) R^(A28)R^(A2) C(CH₃)₂ L_(A532) H R^(A3) C(CH₃)₂ L_(A533) R^(A2) R^(A3) C(CH₃)₂L_(A534) R^(A3) R^(A3) C(CH₃)₂ L_(A535) R^(A14) R^(A3) C(CH₃)₂ L_(A536)R^(A22) R^(A3) C(CH₃)₂ L_(A537) R^(A28) R^(A3) C(CH₃)₂ L_(A538) HR^(A14) C(CH₃)₂ L_(A539) R^(A2) R^(A14) C(CH₃)₂ L_(A540) R^(A3) R^(A14)C(CH₃)₂ L_(A541) R^(A14) R^(A14) C(CH₃)₂ L_(A542) R^(A22) R^(A14)C(CH₃)₂ L_(A543) R^(A28) R^(A14) C(CH₃)₂ L_(A544) H R^(A22) C(CH₃)₂L_(A545) R^(A2) R^(A22) C(CH₃)₂ L_(A546) R^(A3) R^(A22) C(CH₃)₂ L_(A547)R^(A14) R^(A22) C(CH₃)₂ L_(A548) R^(A22) R^(A22) C(CH₃)₂ L_(A549)R^(A28) R^(A22) C(CH₃)₂ L_(A550) H R^(A28) C(CH₃)₂ L_(A551) R^(A2)R^(A28) C(CH₃)₂ L_(A552) R^(A3) R^(A28) C(CH₃)₂ L_(A553) R^(A14) R^(A28)C(CH₃)₂ L_(A554) R^(A22) R^(A28) C(CH₃)₂ L_(A555) R^(A28) R^(A28)C(CH₃)₂ L_(A556) R^(A2) H C(CH₃)₂ L_(A557) R^(A3) H C(CH₃)₂ L_(A558)R^(A14) H C(CH₃)₂ L_(A559) R^(A22) H C(CH₃)₂ L_(A560) R^(A28) H C(CH₃)₂L_(A561) R^(A2) R^(B1) C(CH₃)₂ L_(A562) R^(A3) R^(B1) C(CH₃)₂ L_(A563)R^(A14) R^(B1) C(CH₃)₂ L_(A564) R^(A22) R^(B1) C(CH₃)₂ L_(A565) R^(A28)R^(B1) C(CH₃)₂ L_(A566) R^(A2) R^(B2) C(CH₃)₂ L_(A567) R^(A3) R^(B2)C(CH₃)₂ L_(A568) R^(A14) R^(B2) C(CH₃)₂ L_(A569) R^(A22) R^(B2) C(CH₃)₂L_(A570) R^(A28) R^(B2) C(CH₃)₂ L_(A571) R^(A2) R^(B3) C(CH₃)₂ L_(A572)R^(A3) R^(B3) C(CH₃)₂ L_(A573) R^(A14) R^(B3) C(CH₃)₂ L_(A574) R^(A22)R^(B3) C(CH₃)₂ L_(A575) R^(A28) R^(B3) C(CH₃)₂ L_(A576) R^(A2) R^(B4)C(CH₃)₂ L_(A577) R^(A3) R^(B4) C(CH₃)₂ L_(A578) R^(A14) R^(B4) C(CH₃)₂L_(A579) R^(A22) R^(B4) C(CH₃)₂ L_(A580) R^(A28) R^(B4) C(CH₃)₂ L_(A581)R^(B1) R^(A2) C(CH₃)₂ L_(A582) R^(B1) R^(A3) C(CH₃)₂ L_(A583) R^(B1)R^(A14) C(CH₃)₂ L_(A584) R^(B1) R^(A22) C(CH₃)₂ L_(A585) R^(B1) R^(A28)C(CH₃)₂ L_(A586) R^(B2) R^(A2) C(CH₃)₂ L_(A587) R^(B2) R^(A3) C(CH₃)₂L_(A588) R^(B2) R^(A14) C(CH₃)₂ L_(A589) R^(B2) R^(A22) C(CH₃)₂ L_(A590)R^(B2) R^(A28) C(CH₃)₂ L_(A591) R^(B3) R^(A2) C(CH₃)₂ L_(A592) R^(B3)R^(A3) C(CH₃)₂ L_(A593) R^(B3) R^(A14) C(CH₃)₂ L_(A594) R^(B3) R^(A22)C(CH₃)₂ L_(A595) R^(B3) R^(A28) C(CH₃)₂ L_(A596) R^(B4) R^(A2) C(CH₃)₂L_(A597) R^(B4) R^(A3) C(CH₃)₂ L_(A598) R^(B4) R^(A14) C(CH₃)₂ L_(A599)R^(B4) R^(A22) C(CH₃)₂ L_(A600) R^(B4) R^(A28) C(CH₃)₂ L_(A601) H R^(A2)NCH₃ L_(A602) R^(A2) R^(A2) NCH₃ L_(A603) R^(A3) R^(A2) NCH₃ L_(A604)R^(A14) R^(A2) NCH₃ L_(A605) R^(A22) R^(A2) NCH₃ L_(A606) R^(A28) R^(A2)NCH₃ L_(A607) H R^(A3) NCH₃ L_(A608) R^(A2) R^(A3) NCH₃ L_(A609) R^(A3)R^(A3) NCH₃ L_(A610) R^(A14) R^(A3) NCH₃ L_(A611) R^(A22) R^(A3) NCH₃L_(A612) R^(A28) R^(A3) NCH₃ L_(A613) H R^(A14) NCH₃ L_(A614) R^(A2)R^(A14) NCH₃ L_(A615) R^(A3) R^(A14) NCH₃ L_(A616) R^(A14) R^(A14) NCH₃L_(A617) R^(A22) R^(A14) NCH₃ L_(A618) R^(A28) R^(A14) NCH₃ L_(A619) HR^(A22) NCH₃ L_(A620) R^(A2) R^(A22) NCH₃ L_(A621) R^(A3) R^(A22) NCH₃L_(A622) R^(A14) R^(A22) NCH₃ L_(A623) R^(A22) R^(A22) NCH₃ L_(A624)R^(A28) R^(A22) NCH₃ L_(A625) H R^(A28) NCH₃ L_(A626) R^(A2) R^(A28)NCH₃ L_(A627) R^(A3) R^(A28) NCH₃ L_(A628) R^(A14) R^(A28) NCH₃ L_(A629)R^(A22) R^(A28) NCH₃ L_(A630) R^(A28) R^(A28) NCH₃ L_(A631) R^(A2) HNCH₃ L_(A632) R^(A3) H NCH₃ L_(A633) R^(A14) H NCH₃ L_(A634) R^(A22) HNCH₃ L_(A635) R^(A28) H NCH₃ L_(A636) R^(A2) R^(B1) NCH₃ L_(A637) R^(A3)R^(B1) NCH₃ L_(A638) R^(A14) R^(B1) NCH₃ L_(A639) R^(A22) R^(B1) NCH₃L_(A640) R^(A28) R^(B1) NCH₃ L_(A641) R^(A2) R^(B2) NCH₃ L_(A642) R^(A3)R^(B2) NCH₃ L_(A643) R^(A14) R^(B2) NCH₃ L_(A644) R^(A22) R^(B2) NCH₃L_(A645) R^(A28) R^(B2) NCH₃ L_(A646) R^(A2) R^(B3) NCH₃ L_(A647) R^(A3)R^(B3) NCH₃ L_(A648) R^(A14) R^(B3) NCH₃ L_(A649) R^(A22) R^(B3) NCH₃L_(A650) R^(A28) R^(B3) NCH₃ L_(A651) R^(A2) R^(B4) NCH₃ L_(A652) R^(A3)R^(B) NCH₃ L_(A653) R^(A14) R^(B4) NCH₃ L_(A654) R^(A22) R^(B4) NCH₃L_(A655) R^(A28) R^(B4) NCH₃ L_(A656) R^(A2) R^(B1) NCH₃ L_(A657) R^(A3)R^(B1) NCH₃ L_(A658) R^(A14) R^(B1) NCH₃ L_(A659) R^(A22) R^(B1) NCH₃L_(A660) R^(A28) R^(B1) NCH₃ L_(A651) R^(A2) R^(B2) NCH₃ L_(A662) R^(A3)R^(B2) NCH₃ L_(A663) R^(A14) R^(B2) NCH₃ L_(A664) R^(A22) R^(B2) NCH₃L_(A665) R^(A28) R^(B2) NCH₃ L_(A666) R^(A2) R^(B3) NCH₃ L_(A667) R^(A3)R^(B3) NCH₃ L_(A668) R^(A14) R^(B3) NCH₃ L_(A669) R^(A22) R^(B3) NCH₃L_(A670) R^(A28) R^(B3) NCH₃ L_(A671) R^(A2) R^(B4) NCH₃ L_(A672) R^(A3)R^(B4) NCH₃ L_(A673) R^(A14) R^(B4) NCH₃ L_(A674) R^(A22) R^(B4) NCH₃L_(A675) R^(A28) R^(B4) NCH₃ L_(A676) H R^(A2) N(isobutyl) L_(A677)R^(A2) R^(A2) N(isobutyl) L_(A678) R^(A3) R^(A2) N(isobutyl) L_(A679)R^(A14) R^(A2) N(isobutyl) L_(A680) R^(A22) R^(A2) N(isobutyl) L_(A681)R^(A28) R^(A2) N(isobutyl) L_(A682) H R^(A3) N(isobutyl) L_(A683) R^(A2)R^(A3) N(isobutyl) L_(A684) R^(A3) R^(A3) N(isobutyl) L_(A685) R^(A14)R^(A3) N(isobutyl) L_(A686) R^(A22) R^(A3) N(isobutyl) L_(A687) R^(A28)R^(A3) N(isobutyl) L_(A688) H R^(A14) N(isobutyl) L_(A689) R^(A2)R^(A14) N(isobutyl) L_(A690) R^(A3) R^(A14) N(isobutyl) L_(A691) R^(A14)R^(A14) N(isobutyl) L_(A692) R^(A22) R^(A14) N(isobutyl) L_(A693)R^(A28) R^(A14) N(isobutyl) L_(A694) H R^(A22) N(isobutyl) L_(A695)R^(A2) R^(A22) N(isobutyl) L_(A696) R^(A3) R^(A22) N(isobutyl) L_(A697)R^(A14) R^(A22) N(isobutyl) L_(A698) R^(A22) R^(A22) N(isobutyl)L_(A699) R^(A28) R^(A22) N(isobutyl) L_(A700) H R^(A28) N(isobutyl)L_(A701) R^(A2) R^(A28) N(isobutyl) L_(A702) R^(A3) R^(A28) N(isobutyl)L_(A703) R^(A14) R^(A28) N(isobutyl) L_(A704) R^(A22) R^(A28)N(isobutyl) L_(A705) R^(A28) R^(A28) N(isobutyl) L_(A 706) R^(A2) HN(isobutyl) L_(A707) R^(A3) H N(isobutyl) L_(A708) R^(A14) H N(isobutyl)L_(A709) R^(A22) H N(isobutyl) L_(A710) R^(A28) H N(isobutyl) L_(A711)R^(A2) R^(B1) N(isobutyl) L_(A712) R^(A3) R^(B1) N(isobutyl) L_(A713)R^(A14) R^(B1) N(isobutyl) L_(A714) R^(A22) R^(B1) N(isobutyl) L_(A715)R^(A28) R^(B1) N(isobutyl) L_(A716) R^(A2) R^(B2) N(isobutyl) L_(A717)R^(A3) R^(B2) N(isobutyl) L_(A718) R^(A14) R^(B2) N(isobutyl) L_(A719)R^(A22) R^(B2) N(isobutyl) L_(A720) R^(A28) R^(B2) N(isobutyl) L_(A721)R^(A2) R^(B3) N(isobutyl) L_(A722) R^(A3) R^(B3) N(isobutyl) L_(A723)R^(A14) R^(B3) N(isobutyl) L_(A724) R^(A22) R^(B3) N(isobutyl) L_(A725)R^(A28) R^(B3) N(isobutyl) L_(A726) R^(A2) R^(B4) N(isobutyl) L_(A727)R^(A3) R^(B4) N(isobutyl) L_(A728) R^(A14) R^(B4) N(isobutyl) L_(A729)R^(A22) R^(B4) N(isobutyl) L_(A730) R^(A28) R^(B4) N(isobutyl) L_(A731)R^(B1) R^(A2) N(isobutyl) L_(A732) R^(B1) R^(A3) N(isobutyl) L_(A733)R^(B1) R^(A14) N(isobutyl) L_(A734) R^(B1) R^(A22) N(isobutyl) L_(A735)R^(B1) R^(A28) N(isobutyl) L_(A736) R^(B2) R^(A2) N(isobutyl) L_(A737)R^(B2) R^(A3) N(isobutyl) L_(A738) R^(B2) R^(A14) N(isobutyl) L_(A739)R^(B2) R^(A22) N(isobutyl) L_(A740) R^(B2) R^(A28) N(isobutyl) L_(A741)R^(B3) R^(A2) N(isobutyl) L_(A742) R^(B3) R^(A3) N(isobutyl) L_(A743)R^(B3) R^(A14) N(isobutyl) L_(A744) R^(B3) R^(A22) N(isobutyl) L_(A745)R^(B3) R^(A28) N(isobutyl) L_(A746) R^(B4) R^(A2) N(isobutyl) L_(A747)R^(B4) R^(A3) N(isobutyl) L_(A748) R^(B4) R^(A14) N(isobutyl) L_(A749)R^(B4) R^(A22) N(isobutyl) L_(A750) R^(B4) R^(A28) N(isobutyl)wherein R^(B1) to R^(B4) have the following structures:

In some embodiments of the compound, the compound has a structure ofFormula III, (L_(A))_(n)Ir(L_(B))_(3-n), wherein L_(B) is a bidentateligand and n is 1, 2, or 3.

In some embodiments of the compound having the structure of Formula III,the ligand L_(B) is selected from the group consisting of:

In some embodiments of the compound having the structure of Formula III,the compound is selected from the group consisting of Compound 1 throughCompound 12,750;

wherein each Compound x has the formula Ir(L_(Ak))₂(L_(Bj));

wherein x=750j+k−750, k is an integer from 1 to 750, and j is an integerfrom 1 to 17; and wherein ligands L_(B1) through L_(B17) are defined asfollows:

In some embodiments of the compound, the compound has a structure ofFormula VI, (L_(A))_(m)Pt(L_(C))_(2-m), wherein L_(C) is a bidentateligand, and m is 1, or 2.

In some embodiments of the compound having the structure of Formula VI,m is 1, and L_(A) is connected to L_(C) to form a tetradentate ligand.

According to another aspect of the present disclosure, a first organiclight emitting device comprising: an anode; a cathode, and an organiclayer disposed between the anode and the cathode is disclosed. Theorganic layer comprises a compound comprising a ligand L_(A) of FormulaI.

wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclicring;

wherein R is fused to ring B and has a structure of Formula II,

wherein the wave lines indicate bonds to ring B;

-   -   wherein R¹ represents mono, di, tri, or tetra substitution, or        no substitution;

wherein R² represents mono or di substitution, or no substitution;

wherein X¹, X², X³, and X⁴ are each independently carbon or nitrogen;

wherein at least two adjacent of X¹, X², X³, and X⁴ are carbon and fuseto R;

wherein X is selected from the group consisting of BR′, NR′, PR′, O, S,Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″;

wherein R¹, R², R³, R⁴, R′, and R″ are each independently selected fromthe group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof; and wherein any twoadjacent substituents are optionally joined to form into a ring;

wherein at least one of R³ and R⁴ comprises a chemical group selectedfrom the group consisting of alkyl, cycloalkyl, partially fluorinatedalkyl, partially fluorinated cycloalkyl, and combinations thereof;

wherein L_(A) is coordinated to a metal M;

wherein L_(A) is optionally linked with other ligands to comprise atridentate, tetradentate, pentadentate, or hexadentate ligand; and

wherein M is optionally coordinated to other ligands.

The organic light emitting device disclosed herein can be incorporatedinto one or more of a consumer product, an electronic component module,an organic light-emitting device, and a lighting panel. The organiclayer can be an emissive layer and the compound can be an emissivedopant in some embodiments, while the compound can be a non-emissivedopant in other embodiments.

The organic layer can also include a host. In some embodiments, two ormore hosts are preferred. In some embodiments, the hosts used may be a)bipolar, b) electron transporting, c) hole transporting or d) wide bandgap materials that play little role in charge transport. In someembodiments, the host can include a metal complex. The host can be atriphenylene containing benzo-fused thiophene or benzo-fused furan. Anysubstituent in the host can be an unfused substituent independentlyselected from the group consisting of C_(n)H_(2n+1), OC_(n)H_(2n+1),OAr₁, N(C_(n)H_(2n+1))₂, N(Ar₁)(Ar₂), CH═CH—C_(n)H_(2n+1),C≡C—C_(n)H_(2n+1), Ar₁, Ar₁-Ar₂, and C_(n)H_(2n)—Ar₁, or the host has nosubstitution. In the preceding substituents n can range from 1 to 10;and Ar₁ and Ar₂ can be independently selected from the group consistingof benzene, biphenyl, naphthalene, triphenylene, carbazole, andheteroaromatic analogs thereof. The host can be an inorganic compound.For example a Zn containing inorganic material e.g. ZnS.

The host can be a compound comprising at least one chemical groupselected from the group consisting of triphenylene, carbazole,dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene,azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, andaza-dibenzoselenophene. The host can include a metal complex.

The host can be, but is not limited to, a specific compound selectedfrom the group consisting of:

and combinations thereof. Additional information on possible hosts isprovided below.

According to another aspect of the present disclosure, a formulationcomprising a compound comprising the ligand L_(A) of Formula I, asdefined above, is disclosed. The formulation can include one or morecomponents selected from the group consisting of a solvent, a host, ahole injection material, hole transport material, and an electrontransport layer material, disclosed herein.

Combination with Other Materials

The materials described herein as useful for a particular layer in anorganic light emitting device may be used in combination with a widevariety of other materials present in the device. For example, emissivedopants disclosed herein may be used in conjunction with a wide varietyof hosts, transport layers, blocking layers, injection layers,electrodes and other layers that may be present. The materials describedor referred to below are non-limiting examples of materials that may beuseful in combination with the compounds disclosed herein, and one ofskill in the art can readily consult the literature to identify othermaterials that may be useful in combination.

Conductivity Dopants:

A charge transport layer can be doped with conductivity dopants tosubstantially alter its density of charge carriers, which will in turnalter its conductivity. The conductivity is increased by generatingcharge carriers in the matrix material, and depending on the type ofdopant, a change in the Fermi level of the semiconductor may also beachieved. Hole-transporting layer can be doped by p-type conductivitydopants and n-type conductivity dopants are used in theelectron-transporting layer. Non-limiting examples of the conductivitydopants that may be used in an OLED in combination with materialsdisclosed herein are exemplified below together with references thatdisclose those materials:

EP01617493, EP01968131, EP2020694, EP2684932, US20050139810,US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455,WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 andUS2012146012.

HIL/HTL:

A hole injecting/transporting material to be used in the presentinvention is not particularly limited, and any compound may be used aslong as the compound is typically used as a hole injecting/transportingmaterial. Examples of the material include, but are not limited to: aphthalocyanine or porphyrin derivative; an aromatic amine derivative; anindolocarbazole derivative; a polymer containing fluorohydrocarbon; apolymer with conductivity dopants; a conducting polymer, such asPEDOT/PSS; a self-assembly monomer derived from compounds such asphosphonic acid and silane derivatives; a metal oxide derivative, suchas MoO_(x); a p-type semiconducting organic compound, such as1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and across-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, butnot limit to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting of aromatichydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl,triphenylene, naphthalene, anthracene, phenalene, phenanthrene,fluorene, pyrene, chrysene, perylene, and azulene; the group consistingof aromatic heterocyclic compounds such as dibenzothiophene,dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran,benzothiophene, benzoselenophene, carbazole, indolocarbazole,pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole,oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole,pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine,oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine,benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline,cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine,pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine,benzofuropyridine, furodipyridine, benzothienopyridine,thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine;and the group consisting of 2 to 10 cyclic structural units which aregroups of the same type or different types selected from the aromatichydrocarbon cyclic group and the aromatic heterocyclic group and arebonded to each other directly or via at least one of oxygen atom,nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom,chain structural unit and the aliphatic cyclic group. Each Ar may beunsubstituted or may be substituted by a substituent selected from thegroup consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylicacids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the groupconsisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH)or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but are notlimited to the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40;(Y¹⁰¹-Y¹⁰²) is a bidentate ligand. Y¹⁰¹ and Y¹⁰² are independentlyselected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k′ is aninteger value from 1 to the maximum number of ligands that may beattached to the metal; and k′+k″ is the maximum number of ligands thatmay be attached to the metal.

In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In anotheraspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met isselected from Ir, Pt, Os, and Zn. In a further aspect, the metal complexhas a smallest oxidation potential in solution vs. Fc⁺/Fc couple lessthan about 0.6 V.

Non-limiting examples of the HIL and HTL materials that may be used inan OLED in combination with materials disclosed herein are exemplifiedbelow together with references that disclose those materials:

CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334,EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701,EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765,JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473,TW201139402, U.S. Pat. No. 6,517,957. US20020158242, US20030162053,US20050123751, US20060182993, US20060240279, US20070145888,US20070181874, US20070278938, US20080014464, US20080091025,US20080106190, US20080124572, US20080145707, US20080220265,US20080233434, US20080303417, US2008107919, US20090115320,US20090167161, US2009066235, US2011007385, US20110163302, US2011240968,US2011278551, US2012205642, US2013241401, US20140117329, US2014183517,U.S. Pat. No. 5,061,569, U.S. Pat. No. 5,639,914, WO05075451,WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824,WO2011075644, WO2012177006, WO02013018530, WO2013039073, WO2013087142,WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873,WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791,WO2014104514, WO2014157018.

EBL:

An electron blocking layer (EBL) may be used to reduce the number ofelectrons and/or excitons that leave the emissive layer. The presence ofsuch a blocking layer in a device may result in substantially higherefficiencies, and or longer lifetime, as compared to a similar devicelacking a blocking layer. Also, a blocking layer may be used to confineemission to a desired region of an OLED. In some embodiments, the EBLmaterial has a higher LUMO (closer to the vacuum level) and/or highertriplet energy than the emitter closest to the EBL interface. In someembodiments, the EBL material has a higher LUMO (closer to the vacuumlevel) and or higher triplet energy than one or more of the hostsclosest to the EBL interface. In one aspect, the compound used in EBLcontains the same molecule or the same functional groups used as one ofthe hosts described below.

Host:

The light emitting layer of the organic EL device of the presentinvention preferably contains at least a metal complex as light emittingmaterial, and may contain a host material using the metal complex as adopant material. Examples of the host material are not particularlylimited, and any metal complexes or organic compounds may be used aslong as the triplet energy of the host is larger than that of thedopant. While the Table below categorizes host materials as preferredfor devices that emit various colors, any host material may be used withany dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have thefollowing general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³ and Y¹⁰⁴are independently selected from C, N, O, P, and S; L¹⁰¹ is an anotherligand; k′ is an integer value from 1 to the maximum number of ligandsthat may be attached to the metal; and k′+k″ is the maximum number ofligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms Oand N.

In another aspect, Met is selected from Ir and Pt. In a further aspect,(Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

Examples of organic compounds used as host are selected from the groupconsisting of aromatic hydrocarbon cyclic compounds such as benzene,biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene,anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene,perylene, and azulene; the group consisting of aromatic heterocycliccompounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene,furan, thiophene, benzofuran, benzothiophene, benzoselenophene,carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole,imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole,dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine,triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole,indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole,quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline,naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine,phenothiazine, phenoxazine, benzofuropyridine, furodipyridine,benzothienopyridine, thienodipyridine, benzoselenophenopyridine, andselenophenodipyridine; and the group consisting of 2 to 10 cyclicstructural units which are groups of the same type or different typesselected from the aromatic hydrocarbon cyclic group and the aromaticheterocyclic group and are bonded to each other directly or via at leastone of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorusatom, boron atom, chain structural unit and the aliphatic cyclic group.Each option within each group may be unsubstituted or may be substitutedby a substituent selected from the group consisting of deuterium,halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof.

In one aspect, the host compound contains at least one of the followinggroups in the molecule:

wherein each of R¹⁰¹ to R¹⁰⁷ is independently selected from the groupconsisting of hydrogen, deuterium, halide, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof, and when it is aryl orheteroaryl, it has the similar definition as Ar's mentioned above. k isan integer from 0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. X¹⁰¹to X¹⁰⁸ is selected from C (including CH) or N.Z¹⁰¹ and Z¹⁰² is selected from NR¹⁰¹, O, or S.Non-limiting examples of the Host materials that may be used in an OLEDin combination with materials disclosed herein are exemplified belowtogether with references that disclose those materials:

EP2034538, EP2034538A, EP2757608, JP2007254297. KR20100079458,KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553,US20050238919, US20060280965, US20090017330, US20090030202,US20090167162, US20090302743, US20090309488, US20100012931,US20100084966, US20100187984, US2010187984, US2012075273, US2012126221,US2013009543, US2013105787, US2013175519, US2014001446, US20140183503,US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234,WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966,WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833,WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244,WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644,WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404,WO2014142472.

Emitter:

An emitter example is not particularly limited, and any compound may beused as long as the compound is typically used as an emitter material.Examples of suitable emitter materials include, but are not limited to,compounds which can produce emissions via phosphorescence, fluorescence,thermally activated delayed fluorescence, i.e., TADF (also referred toas E-type delayed fluorescence), triplet-triplet annihilation, orcombinations of these processes.

Non-limiting examples of the emitter materials that may be used in anOLED in combination with materials disclosed herein are exemplifiedbelow together with references that disclose those materials:CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526,EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907,EP2730583, JP2012074444, JP2013110263, JP4478555. KR1020090133652,KR20120032054, KR20130043460, TW201332980, U.S. Pat. No. 6,699,599, U.S.Pat. No. 6,916,554, US20010019782, US20020034656. US20030068526,US20030072964, US20030138657, US20050123788, US20050244673,US2005123791, US2005260449, US20060008670, US20060065890, US20060127696,US20060134459, US20060134462, US20060202194, US20060251923,US20070034863, US20070087321, US20070103060, US20070111026,US20070190359, US20070231600, US2007034863, US2007104979, US2007104980,US2007138437, US2007224450, US2007278936, US20080020237, US20080233410,US20080261076, US20080297033, US200805851, US2008161567, US2008210930,US20090039776, US20090108737, US20090115322, US20090179555,US2009085476, US2009104472, US20100090591, US20100148663, US20100244004,US20100295032, US2010102716, US2010105902, US2010244004, US2010270916,US20110057559, US20110108822, US20110204333, US2011215710, US2011227049,US2011285275, US2012292601, US20130146848, US2013033172, US2013165653,US2013181190, US2013334521, US20140246656, US2014103305. U.S. Pat. No.6,303,238, U.S. Pat. No. 6,413,656. U.S. Pat. No. 6,653,654. U.S. Pat.No. 6,670,645, U.S. Pat. No. 6,687,266, U.S. Pat. No. 6,835,469, U.S.Pat. No. 6,921,915, U.S. Pat. No. 7,279,704, U.S. Pat. No. 7,332,232,U.S. Pat. No. 7,378,162, U.S. Pat. No. 7,534,505, U.S. Pat. No.7,675,228. U.S. Pat. No. 7,728,137, U.S. Pat. No. 7,740,957, U.S. Pat.No. 7,759,489, U.S. Pat. No. 7,951,947, U.S. Pat. No. 8,067,099, U.S.Pat. No. 8,592,586. U.S. Pat. No. 8,871,361, WO06081973, WO06121811,WO07018067, WO07108362, WO07115970, WO07115981, WO08035571,WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584,WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281,WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029,WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471,WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982,WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holesand/or excitons that leave the emissive layer. The presence of such ablocking layer in a device may result in substantially higherefficiencies and/or longer lifetime as compared to a similar devicelacking a blocking layer. Also, a blocking layer may be used to confineemission to a desired region of an OLED. In some embodiments, the HBLmaterial has a lower HOMO (further from the vacuum level) and or highertriplet energy than the emitter closest to the HBL interface. In someembodiments, the HBL material has a lower HOMO (further from the vacuumlevel) and or higher triplet energy than one or more of the hostsclosest to the HBL interface.

In one aspect, compound used in HBL contains the same molecule or thesame functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of thefollowing groups in the molecule:

wherein k is an integer from 1 to 20; L¹⁰¹ is an another ligand, k′ isan integer from 1 to 3.ETL:

Electron transport layer (ETL) may include a material capable oftransporting electrons. Electron transport layer may be intrinsic(undoped), or doped. Doping may be used to enhance conductivity.Examples of the ETL material are not particularly limited, and any metalcomplexes or organic compounds may be used as long as they are typicallyused to transport electrons.

In one aspect, compound used in ETL contains at least one of thefollowing groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen,deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof, when it is aryl or heteroaryl, it has the similar definition asAr's mentioned above. Ar¹ to Ar³ has the similar definition as Ar'smentioned above. k is an integer from 1 to 20. X¹⁰¹ to X¹⁰⁸ is selectedfrom C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but notlimit to the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinatedto atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer valuefrom 1 to the maximum number of ligands that may be attached to themetal.

Non-limiting examples of the ETL materials that may be used in an OLEDin combination with materials disclosed herein are exemplified belowtogether with references that disclose those materials: CN103508940,EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918,JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977,US2007018155, US20090101870, US20090115316, US20090140637,US20090179554, US2009218940, US2010108990, US2011156017, US2011210320,US2012193612, US2012214993, US2014014925, US2014014927, US20140284580,U.S. Pat. No. 6,656,612, U.S. Pat. No. 8,415,031, WO2003060956,WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770,WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499,WO2014104535.

Charge Generation Layer (CGL)

In tandem or stacked OLEDs, the CGL plays an essential role in theperformance, which is composed of an n-doped layer and a p-doped layerfor injection of electrons and holes, respectively. Electrons and holesare supplied from the CGL and electrodes. The consumed electrons andholes in the CGL are refilled by the electrons and holes injected fromthe cathode and anode, respectively; then, the bipolar currents reach asteady state gradually. Typical CGL materials include n and pconductivity dopants used in the transport layers.

In any above-mentioned compounds used in each layer of the OLED device,the hydrogen atoms can be partially or fully deuterated. Thus, anyspecifically listed substituent, such as, without limitation, methyl,phenyl, pyridyl, etc. may be undeuterated, partially deuterated, andfully deuterated versions thereof. Similarly, classes of substituentssuch as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc.also may be undeuterated, partially deuterated, and fully deuteratedversions thereof.

EXPERIMENTAL

Materials Synthesis

All reactions were carried out under nitrogen protections unlessspecified otherwise. All solvents for reactions are anhydrous and usedas received from commercial sources.

Synthesis of Compound 3676

Synthesis of 4-(3,5-dimethylphenyl)-7-isopropylthieno[3,2-d]pyrimidine

4-chloro-7-isopropylthieno[3,2-d]pyrimidine (4.50 g, 21.2 mmol).Pd(PPh₃)₄ (0.73 g, 0.64 mmol), potassium carbonate (7.31 g, 52.9 mmol),tetrahydrofuran (THF) (200 ml), and water (50.0 ml) were combined in aflask. The mixture was degassed by bubbling nitrogen gas for 15 minutesand the reaction was then heated to reflux overnight. The reaction wasextracted with ethyl acetate and washed with brine, dried with sodiumsulfate, filtered and concentrated down. The brown oil was purified withsilica gel using DCM to 90/10 DCM % ethyl acetate solvent system. Theorange oil was further purified with silica gel using 75/25 hept/ethylacetate solvent system to get 5.50 g of a white solid for a 90% yield.

Synthesis of the Ir(III) Dimer

4-(3,5-dimethylphenyl)-7-isopropylthieno[3,2-d]pyrimidine (3.07 g, 10.9mmol) was inserted in a flask and was solubilized in 2-ethoxyethanol (40mL) and Water (13 mL). The mixture was degassed by bubbling nitrogen gasfor 15 minutes then IrCl₃H₈O₄ (1.15 g, 3.10 mmol) was inserted. Thereaction was heated at 105° C. for 24 hours under nitrogen. The reactionwas cooled down to room temperature, diluted with 10 mL of MeOH,filtered and washed with MeOH to obtain 1.6 g of a solid for a 65%yield.

Synthesis of Compound 3676

The Ir(III) dimer (1.00 g, 0.63 mmol), 3,7-diethylnonane-4,6-dione (1.34g, 6.33 mmol) and 2-ethoxyethanol (15 ml) were combined in a flask.Nitrogen was bubbled into the suspension for 15 minutes and potassiumcarbonate (0.87 g, 6.33 mmol) was added. The rxn was stirred at roomtemperature overnight. The mixture was filtered through celite usingdichloromethane (DCM) and the filtrate was concentrated down. The solidwas triturated in 100 mL of MeOH and the solid was filtered off. Thesolid was purified with silica gel (Pre-treated with Triethylamine)using 95/5 to 90/10 hept/DCM to afford 0.45 g of the title compound (37%yield).

Synthesis of Compound 6796

Synthesis of 6,7-dichloro-4-(3 dimethylphenyl)thieno[3,2-d]pyrimidine

4,6,7-trichlorothieno[3,2-d]pyrimidine (12.0 g, 50.1 mmol),(3,5-dimethylphenyl)boronic acid (8.27 g, 55.1 mmol), potassiumcarbonate (17.3 g, 125 mmol), THF (300 mL), and Water (75 mL) werecombined in a flask. The solution was purged with nitrogen for 15 minthen palladium tetrakis (1.74 g, 1.503 mmol) was added. The reaction washeated to reflux under nitrogen overnight. The reaction mixture wasextracted with ethyl acetate (3 times), then washed with Brine andWater. The yellow solid was purified with silica gel using 90/10hept/EtOac as the solvent system to afford a white solid. The sample wasfurther purified with silica gel using DCM to 95/5 DCM/EtOac as thesolvent system to get 8.4 g of a white solid for a 54% yield.

Synthesis of4-(3,5-dimethylphenyl)-6,7-bis(3,3,3-trifluoropropyl)thieno[3,2-d]pyrimidine

6,7-dichloro-4-(3,5-dimethylphenyl)thieno[3,2-d]pyrimidine (5.00 g, 16.2mmol), palladium(II) acetate (0.73 g, 3.23 mmol), and2′-(dicyclohexylphosphanyl)-N2,N2,N6,N6-tetramethyl-[1,1′-biphenyl]-2,6-diamine(CPhos) (2.82 g, 6.47 mmol) were combined in an oven dried flask. Thesystem was purged with nitrogen then THF (50 mL) was added via syringe.The reaction was stirred for 15 min, then(3,3,3-trifluoropropyl)zinc(II) iodide (300 mL, 64.7 mmol) was addedquickly via syringe. The reaction was stirred at room temperatureovernight and then it was quenched with sodium bicarbonate solution Themixture was extracted 3 times with ethyl acetate and the suspension wasfiltered through celite to remove the insoluble solids. The organicphase was washed twice with brine, dried with sodium sulfate, filteredand concentrated down to a brown oil. The crude product was purifiedwith silica gel using 90/10 heptanes/ethyl acetate to get a light brownoil. The sample was further purified with C18 columns using 70/30 to90/10 acetonitrile/water as the solvent system to afford 2.56 g of awhite solid for a 37% yield.

Synthesis of the Ir(III) Dimer

4-(3,5-dimethylphenyl)-6,7-bis(3,3,3-trifluoropropyl)thieno[3,2-d]pyrimidine(2.86 g, 6.61 mmol), 2-ethoxy ethanol (24 mL) and water (8 mL) werecombined in a flask. Nitrogen was bubbled into the reaction for 15minutes, then IrCl₃H₈O₄ (0.70 g, 1.89 mmol) was added. The reaction washeated at 105° C. overnight under nitrogen. The reaction was cooled anddiluted with 10 mL of MeOH, filtered and washed with MeOH to afford 2.28g (Quantitative Yield) of an orange-red solid.

Synthesis of Compound 6796

The Ir(III) dimer (2.10 g, 1.59 mmol),3,7-diethyl-5-methylnonane-4,6-dione (4.0 ml, 15.9 mmol) and2-ethoxyethanol (30 ml) were combined in a flask. Nitrogen was bubbledinto the suspension for 15 minutes then potassium carbonate (2.20 g,15.9 mmol) was added. The reaction was stirred at room temperatureovernight. Upon completion of the reaction, the reaction was diluted inDCM and was filtered through celite. The red oil was triturated in 75 mLof hot MeOH, cooled to room temperature and then filtered off. The solidwas purified with silica gel (Pre-treated with Triethylamine) using 95/5to 85/15 of heptanes/DCM solvent system to afford 1.41 g of the titlecompound (35% yield).

Synthesis of Compound 6841

Synthesis of6-bromo-4-(3,5-dimethylphenyl)-7-isopropylthieno[3,2-d]pyrimidine

4-(3,5-dimethylphenyl)-7-isopropylthieno[3,2-d]pyrimidine (5.00 g, 17.7mmol) was added to an oven-dried flask. The system was evacuated andpurged with nitrogen three times. THF (200 mL) was added and thesolution was cooled to −70° C., then 2.5 M butyllithium (8.5 mL, 21.3mmol) was added dropwise. The reaction was stirred for three hours atthis temperature, then dibromine (1.0 mL, 19.5 mmol) was added dropwise.The reaction was stirred for 30 minutes at −70° C. then it was allowedwarm up to room temperature and stirred overnight. The mixture wasquenched with water and extracted with ethyl acetate and washed twicewith brine, dried with sodium sulfate, filtered and concentrated down toan orange-yellow solid. The crude product was purified with silica gelusing 95/5 to 90/10 heptane/EtOac solvent system to obtain an off-whitesolid. The purification with silica gel was repeated using 97.5/2.5 to95/5 heptane/EtOac solvent system to get 5.10 g of a white solid for an80% yield.

Synthesis of4-(3,5-dimethylphenyl)-7-isopropyl-6-(3,3,3-trifluoro-2,2-dimethylpropyl)thieno[3,2-d]pyrimidine

6-bromo-4-(3,5-dimethylphenyl)-7-isopropylthieno[3,2-d]pyrimidine (4.50g, 12.5 mmol), palladium(II) acetate (0.11 g, 0.50 mmol), and2′-(dicyclohexylphosphanyl)-N2,N2,N6,N6-tetramethyl-[1,1′-biphenyl]-2,6-diamine(Cphos) (0.44 g, 1.00 mmol) were combined in an oven dried flask. Thesolids were solubilized in THF (50 mL) and the reaction was stirred for15 min, then (3,3,3-trifluoro-2,2-dimethylpropyl)zinc(II) bromide (110ml, 24.9 mmol) was added via syringe and the mixture was stirredovernight. The reaction was quenched with sodium bicarbonate solution,extracted with ethyl acetate (3 times). The combined organics werewashed twice with brine, dried with sodium sulfate, filtered andconcentrated down. The crude product was purified with silica gel using85/15 heptane/ethyl acetate to get 5.0 g of a brown oil. The product waspurified again with silica gel using 97.5/2.5 to 95/5 heptane/ethylacetate to get 4.1 g of a clear oil which changed to a white solid foran 80% yield.

Synthesis of the Ir(III) Dimer

4-(3,5-dimethylphenyl)-7-isopropyl-6-(3,3,3-trifluoro-2,2-dimethylpropyl)thieno[3,2-d]pyrimidine(3.84 g, 9.44 mmol), 2-ethoxyethanol (34 mL), and water (11 mL werecombined in a flask. The mixture was degassed by bubbling nitrogen gasfor 15 minutes, then IrCl₃H₈O₄ (1.00 g, 2.70 mmol) was added. Thereaction was heated at 105° C. for 24 hours. The reaction was cooleddown to room temperature, diluted with 30 ml MeOH, then the product wasfiltered and washed with MeOH to afford 2.50 g (Quantitative yield).

Synthesis of Compound 6841

The Ir(II) dimer (2.00 g, 1.58 mmol),3,7-diethyl-5-methylnonane-4,6-dione (3.58 g, 15.8 mmol) and2-ethoxyethanol (30 ml) were combined in a flask. Nitrogen was bubbledinto the suspension for 15 min. and then potassium carbonate (2.18 g,15.8 mmol) was added. The reaction was stirred at room temperatureovernight. The mixture was filtered through celite using DCM and thefiltrate was concentrated down. The solid was triturated in 100 mL ofMeOH and the solid was filtered off. The solid was purified with silicagel (Pre-treated with Triethylamine) using 90/10 hept/DCM to afford 1.20g of the title compound (31% yield).

Synthesis of Compound 6836

The Ir(III) dimer (1.80 g, 1.14 mmol),3,7-diethyl-5-methylnonane-4,6-dione (2.9 mL, 11.4 mmol) and2-ethoxyethanol (25 ml) were combined in a flask. Nitrogen was bubbledinto the suspension for 15 minutes and then potassium carbonate (1.57 g,11.4 mmol) was added. The reaction was stirred at room temperatureovernight. The mixture was filtered through celite using DCM and thefiltrate was concentrated down. The solid was triturated in 100 mL ofMeOH and was filtered off. The crude product was purified with silicagel (Pre-treated with Triethylamine) using 95/5 to 90/10 heptanes/DCM toafford 1.20 g of the title compound (54% yield).

Synthesis of Comparative Compound 1

Synthesis of the Ir(III) Dimer

7-(3,5-dimethylphenyl)thieno[2,3-c]pyridine (2.063 g, 8.62 mmol) wassolubilized in Ethoxyethanol (26 mL) and Water (9 mL). The mixture wasdegassed by bubbling nitrogen gas for 15 minutes and then iridium(II)chloride trihydrate (0.80 g, 2.269 mmol) was inserted and the reactionwas heated at 105° C. for 24 hours. The reaction was cooled down to roomtemperature, diluted with 10 mL of MeOH, filtered and washed with MeOHto afford 1.20 g (75% yield) of the product.

Synthesis of Comparative Compound 1

The Ir(III) Dimer (1.15 g, 0.82 mmol), 3,7-diethylnonane-4,6-dione (1.30g, 6.12 mmol) and 2-ethoxyethanol (14 mL) were combined and the mixturewas purged with nitrogen for 15 minutes Potassium carbonate (0.85 g,6.12 mmol) was added and the reaction was stirred at room temperatureovernight. The mixture was solubilized in DCM and filtered through a padof Celite. The solvent were rotovaped down and the mixture wastriturated from methanol and filtered. The crude material was furtherpurified via column chromatography (pre-treated with triethylamine)using a Heptanes % DCM (95/5) solvent system. The product was thenrecrystallized from a DCM/MeOH mixture to afford 1.30 g (90%/o yield) ofan orange powder.

Device Examples

All example devices were fabricated by high vacuum (<10⁻⁷ Torr) thermalevaporation. The anode electrode was 1150 Å of indium tin oxide (ITO).The cathode consisted of 10 Å of Liq (8-hydroxyquinoline lithium)followed by 1,000 Å of Al. All devices were encapsulated with a glasslid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H₂Oand O₂) immediately after fabrication, and a moisture getter wasincorporated inside the package. The organic stack of the deviceexamples consisted of sequentially, from the ITO surface, 100 Å of LG101(purchased from LG chem) as the hole injection layer (HIL); 400 Å of HTMas a hole transporting layer (HTL); 300 Å of an emissive layer (EML)containing Compound H as a host (a stability dopant (SD) (18%), andComparative Compound 1 or Compounds 3676, 6836, and 6841 as the emitter(3%); 100 Å of Compound H as a blocking layer; and 350 Å of Liq(8-hydroxyquinoline lithium) doped with 40% of ETM as the ETL. Theemitter was selected to provide the desired color, efficiency andlifetime. The stability dopant (SD) was added to theelectron-transporting host to help transport positive charge in theemissive layer. The Comparative Example device was fabricated similarlyto the device examples except that Comparative Compound 1 was used asthe emitter in the EML. Table 3 below shows the device layer thicknessand materials. The chemical structures of the materials used in thedevices are shown in Table 5 below.

The device performance data are summarized in Table 4 below. Inventivecompounds have much longer lifetime vs. comparative compound 1. AlsoCompounds 3676, 6836, and 6841 have superior performance to ComparativeCompound 1 in color saturation as a red shift of 28 to 38 nm wasobserved. Moreover, the inventive compounds afforded either similar orhigher EQE than Comparative Compound 1.

TABLE 3 Device layer materials and thicknesses Layer Material Thickness[Å] Anode ITO 1150 HIL LG101 (LG Chem) 100 HTL HTM 400 EML Compound H:SD 18%: 300 Emitter 3% BL Compound H 100 ETL Liq: ETM 40% 350 EIL Liq 10Cathode Al 1000

TABLE 4 Device performance data At 10 mA/cm² At 80 mA/cm2 Device 1931CIE λ max FWHM Voltage EQE LT_(95%) Example Emitter x y [nm] [nm] [V][%] [h] Example 1 Compound 0.649 0.349 618 54 1.00 1.04 11.5 6841Example 2 Compound 0.650 0.348 617 59 1.00 0.92 9.82 6836 Example 3Compound 0.629 0.369 608 55 1.03 1.00 7.91 3676 CE1 Comparative 0.5470.451 580 48 1.00 1.00 1 Compound 1

TABLE 5 Materials used in the OLED devices

COMPOUND H

  SD

Comparative Compound 1

  HTM

  ETM

  Liq

Compound 6841

Compound 6836

Compound 3676

It is understood that the various embodiments described herein are byway of example only, and are not intended to limit the scope of theinvention. For example, many of the materials and structures describedherein may be substituted with other materials and structures withoutdeviating from the spirit of the invention. The present invention asclaimed may therefore include variations from the particular examplesand preferred embodiments described herein, as will be apparent to oneof skill in the art. It is understood that various theories as to whythe invention works are not intended to be limiting.

We claim:
 1. A compound comprising a ligand L_(A) of Formula I:

wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclicring; wherein R is fused to ring B and has a structure of Formula II:

wherein the wave lines indicate bonds to ring B; wherein R¹ representsmono, di, tri, or tetra substitution, or no substitution; wherein R²represents mono or di substitution, or no substitution; wherein X¹, X²,X³, and X⁴ are each independently carbon or nitrogen; wherein at leasttwo adjacent of X¹, X², X³, and X⁴ are carbon and fuse to R; wherein Xis selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O,S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; wherein R¹, R², R³, R⁴, R′, and R″are each independently selected from the group consisting of hydrogen,deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof; and wherein any two adjacent substituents are optionally joinedto form into a ring; wherein at least one of R³ and R⁴ comprises achemical group selected from the group consisting of alkyl, cycloalkyl,partially fluorinated alkyl, partially fluorinated cycloalkyl, andcombinations thereof; wherein the ligand L_(A) is coordinated to a metalM; wherein the ligand L_(A) is optionally linked with other ligands tocomprise a tridentate, tetradentate, pentadentate, or hexadentateligand; and wherein M is optionally coordinated to other ligands.
 2. Thecompound of claim 1, wherein M is selected from the group consisting ofIr, Rh, Re, Ru, Os, Pt, Au, and Cu.
 3. The compound of claim 1, whereinthe ligand L_(A) is selected from the group consisting of:


4. The compound of claim 1, wherein the ligand L_(A) is:


5. The compound of claim 1, wherein at least one of R³ and R⁴ is achemical group selected from the group consisting of partiallyfluorinated alkyl, partially fluorinated cycloalkyl, and combinationsthereof.
 6. The compound of claim 1, wherein R³ and R⁴ are not hydrogen.7. The compound of claim 1, wherein at least one of X¹, X², X³, and X⁴is nitrogen.
 8. The compound of claim 1, wherein at least one of R³ andR⁴ is selected from the group consisting of:


9. The compound of claim 1, wherein R³ and R⁴ are joined to form a ringstructure selected from the group consisting of:


10. The compound of claim 1, wherein the ligand L_(A) is selected fromthe group consisting of:


11. The compound of claim 8, wherein the ligand L_(A) is selected fromthe group consisting of L_(A1) through L_(A750) defined as follows:L_(A1) through L_(A375) are based on a structure of Formula IV,

in which R³, R⁴, and X are defined as: Ligand R³ R⁴ X L_(A1) H R^(A2) OL_(A2) R^(A2) R^(A2) O L_(A3) R^(A3) R^(A2) O L_(A4) R^(A14) R^(A2) OL_(A5) R^(A22) R^(A2) O L_(A6) R^(A28) R^(A2) O L_(A7) H R^(A3) O L_(A8)R^(A2) R^(A3) O L_(A9) R^(A3) R^(A3) O L_(A10) R^(A14) R^(A3) O L_(A11)R^(A22) R^(A3) O L_(A12) R^(A28) R^(A3) O L_(A13) H R^(A14) O L_(A14)R^(A2) R^(A14) O L_(A15) R^(A3) R^(A14) O L_(A16) R^(A14) R^(A14) OL_(A17) R^(A22) R^(A14) O L_(A18) R^(A28) R^(A14) O L_(A19) H R^(A22) OL_(A20) R^(A2) R^(A22) O L_(A21) R^(A3) R^(A22) O L_(A22) R^(A14)R^(A22) O L_(A23) R^(A22) R^(A22) O L_(A24) R^(A28) R^(A22) O L_(A25) HR^(A28) O L_(A26) R^(A2) R^(A28) O L_(A27) R^(A3) R^(A28) O L_(A28)R^(A14) R^(A28) O L_(A29) R^(A22) R^(A28) O L_(A30) R^(A28) R^(A28) OL_(A31) R^(A2) H O L_(A32) R^(A3) H O L_(A33) R^(A14) H O L_(A34)R^(A22) H O L_(A35) R^(A28) H O L_(A36) R^(A2) R^(B1) O L_(A37) R^(A3)R^(B1) O L_(A38) R^(A14) R^(B1) O L_(A39) R^(A22) R^(B1) O L_(A40)R^(A28) R^(B1) O L_(A41) R^(A2) R^(B2) O L_(A42) R^(A3) R^(B2) O L_(A43)R^(A14) R^(B2) O L_(A44) R^(A22) R^(B2) O L_(A45) R^(A28) R^(B2) OL_(A46) R^(A2) R^(B3) O L_(A47) R^(A3) R^(B3) O L_(A48) R^(A14) R^(B3) OL_(A49) R^(A22) R^(B3) O L_(A50) R^(A28) R^(B3) O L_(A51) R^(A2) R^(B4)O L_(A52) R^(A3) R^(B4) O L_(A53) R^(A14) R^(B4) O L_(A54) R^(A22)R^(B4) O L_(A55) R^(A28) R^(B4) O L_(A56) R^(B1) R^(A2) O L_(A57) R^(B1)R^(A3) O L_(A58) R^(B1) R^(A14) O L_(A59) R^(B1) R^(A22) O L_(A60)R^(B1) R^(A28) O L_(A61) R^(B2) R^(A2) O L_(A62) R^(B2) R^(A3) O L_(A63)R^(B2) R^(A14) O L_(A64) R^(B2) R^(A22) O L_(A65) R^(B2) R^(A28) OL_(A66) R^(B3) R^(A2) O L_(A67) R^(B3) R^(A3) O L_(A68) R^(B3) R^(A14) OL_(A69) R^(B3) R^(A22) O L_(A70) R^(B3) R^(A28) O L_(A71) R^(B4) R^(A2)O L_(A72) R^(B4) R^(A3) O L_(A73) R^(B4) R^(A14) O L_(A74) R^(B4)R^(A22) O L_(A75) R^(B4) R^(A28) O L_(A76) H R^(A2) S L_(A77) R^(A2)R^(A2) S L_(A78) R^(A3) R^(A2) S L_(A79) R^(A14) R^(A2) S L_(A80)R^(A22) R^(A2) S L_(A81) R^(A28) R^(A2) S L_(A82) H R^(A3) S L_(A83)R^(A2) R^(A3) S L_(A84) R^(A3) R^(A3) S L_(A85) R^(A14) R^(A3) S L_(A86)R^(A22) R^(A3) S L_(A87) R^(A28) R^(A3) S L_(A88) H R^(A14) S L_(A89)R^(A2) R^(A14) S L_(A90) R^(A3) R^(A14) S L_(A91) R^(A14) R^(A14) SL_(A92) R^(A22) R^(A14) S L_(A93) R^(A28) R^(A14) S L_(A94) H R^(A22) SL_(A95) R^(A2) R^(A22) S L_(A96) R^(A3) R^(A22) S L_(A97) R^(A14)R^(A22) S L_(A98) R^(A22) R^(A22) S L_(A99) R^(A28) R^(A22) S L_(A100) HR^(A28) S L_(A101) R^(A2) R^(A28) S L_(A102) R^(A3) R^(A28) S L_(A103)R^(A14) R^(A28) S L_(A104) R^(A22) R^(A28) S L_(A105) R^(A28) R^(A28) SL_(A106) R^(A2) H S L_(A107) R^(A3) H S L_(A108) R^(A14) H S L_(A109)R^(A22) H S L_(A110) R^(A28) H S L_(A111) R^(A2) R^(B1) S L_(A112)R^(A3) R^(B1) S L_(A113) R^(A14) R^(B1) S L_(A114) R^(A22) R^(B1) SL_(A115) R^(A28) R^(B1) S L_(A116) R^(A2) R^(B2) S L_(A117) R^(A3)R^(B2) S L_(A118) R^(A14) R^(B2) S L_(A119) R^(A22) R^(B2) S L_(A120)R^(A28) R^(B2) S L_(A121) R^(A2) R^(B3) S L_(A122) R^(A3) R^(B3) SL_(A123) R^(A14) R^(B3) S L_(A124) R^(A22) R^(B3) S L_(A125) R^(A28)R^(B3) S L_(A126) R^(A2) R^(B4) S L_(A127) R^(A3) R^(B4) S L_(A128)R^(A14) R^(B4) S L_(A129) R^(A22) R^(B4) S L_(A130) R^(A28) R^(B4) SL_(A131) R^(B1) R^(A2) S L_(A132) R^(B1) R^(A3) S L_(A133) R^(B1)R^(A14) S L_(A134) R^(B1) R^(A22) S L_(A135) R^(B1) R^(A28) S L_(A136)R^(B2) R^(A2) S L_(A137) R^(B2) R^(A3) S L_(A138) R^(B2) R^(A14) SL_(A139) R^(B2) R^(A22) S L_(A140) R^(B2) R^(A28) S L_(A141) R^(B3)R^(A2) S L_(A142) R^(B3) R^(A3) S L_(A143) R^(B3) R^(A14) S L_(A144)R^(B3) R^(A22) S L_(A145) R^(B3) R^(A28) S L_(A146) R^(B4) R^(A2) SL_(A147) R^(B4) R^(A3) S L_(A148) R^(B4) R^(A14) S L_(A149) R^(B4)R^(A22) S L_(A150) R^(B4) R^(A28) S L_(A151) H R^(A2) C(CH₃)₂ L_(A152)R^(A2) R^(A2) C(CH₃)₂ L_(A153) R^(A3) R^(A2) C(CH₃)₂ L_(A154) R^(A14)R^(A2) C(CH₃)₂ L_(A155) R^(A22) R^(A2) C(CH₃)₂ L_(A156) R^(A28) R^(A2)C(CH₃)₂ L_(A157) H R^(A3) C(CH₃)₂ L_(A158) R^(A2) R^(A3) C(CH₃)₂L_(A159) R^(A3) R^(A3) C(CH₃)₂ L_(A160) R^(A14) R^(A3) C(CH₃)₂ L_(A161)R^(A22) R^(A3) C(CH₃)₂ L_(A162) R^(A28) R^(A3) C(CH₃)₂ L_(A163) HR^(A14) C(CH₃)₂ L_(A164) R^(A2) R^(A14) C(CH₃)₂ L_(A165) R^(A3) R^(A14)C(CH₃)₂ L_(A166) R^(A14) R^(A14) C(CH₃)₂ L_(A167) R^(A22) R^(A14)C(CH₃)₂ L_(A168) R^(A28) R^(A14) C(CH₃)₂ L_(A169) H R^(A22) C(CH₃)₂L_(A170) R^(A2) R^(A22) C(CH₃)₂ L_(A171) R^(A3) R^(A22) C(CH₃)₂ L_(A172)R^(A14) R^(A22) C(CH₃)₂ L_(A173) R^(A22) R^(A22) C(CH₃)₂ L_(A174)R^(A28) R^(A22) C(CH₃)₂ L_(A175) H R^(A28) C(CH₃)₂ L_(A176) R^(A2)R^(A28) C(CH₃)₂ L_(A177) R^(A3) R^(A28) C(CH₃)₂ L_(A178) R^(A14) R^(A28)C(CH₃)₂ L_(A179) R^(A22) R^(A28) C(CH₃)₂ L_(A180) R^(A28) R^(A28)C(CH₃)₂ L_(A181) R^(A2) H C(CH₃)₂ L_(A182) R^(A3) H C(CH₃)₂ L_(A183)R^(A14) H C(CH₃)₂ L_(A184) R^(A22) H C(CH₃)₂ L_(A185) R^(A28) H C(CH₃)₂L_(A186) R^(A2) R^(B1) C(CH₃)₂ L_(A187) R^(A3) R^(B1) C(CH₃)₂ L_(A188)R^(A14) R^(B1) C(CH₃)₂ L_(A189) R^(A22) R^(B1) C(CH₃)₂ L_(A190) R^(A28)R^(B1) C(CH₃)₂ L_(A191) R^(A2) R^(B2) C(CH₃)₂ L_(A192) R^(A3) R^(B2)C(CH₃)₂ L_(A193) R^(A14) R^(B2) C(CH₃)₂ L_(A194) R^(A22) R^(B2) C(CH₃)₂L_(A195) R^(A28) R^(B2) C(CH₃)₂ L_(A196) R^(A2) R^(B3) C(CH₃)₂ L_(A197)R^(A3) R^(B3) C(CH₃)₂ L_(A198) R^(A14) R^(B3) C(CH₃)₂ L_(A199) R^(A22)R^(B3) C(CH₃)₂ L_(A200) R^(A28) R^(B3) C(CH₃)₂ L_(A201) R^(A2) R^(B4)C(CH₃)₂ L_(A202) R^(A3) R^(B4) C(CH₃)₂ L_(A203) R^(A14) R^(B4) C(CH₃)₂L_(A204) R^(A22) R^(B4) C(CH₃)₂ L_(A205) R^(A28) R^(B4) C(CH₃)₂ L_(A206)R^(B1) R^(A2) C(CH₃)₂ L_(A207) R^(B1) R^(A3) C(CH₃)₂ L_(A208) R^(B1)R^(A14) C(CH₃)₂ L_(A209) R^(B1) R^(A22) C(CH₃)₂ L_(A210) R^(B1) R^(A28)C(CH₃)₂ L_(A211) R^(B2) R^(A2) C(CH₃)₂ L_(A212) R^(B2) R^(A3) C(CH₃)₂L_(A213) R^(B2) R^(A14) C(CH₃)₂ L_(A214) R^(B2) R^(A22) C(CH₃)₂ L_(A215)R^(B2) R^(A28) C(CH₃)₂ L_(A216) R^(B3) R^(A2) C(CH₃)₂ L_(A217) R^(B3)R^(A3) C(CH₃)₂ L_(A218) R^(B3) R^(A14) C(CH₃)₂ L_(A219) R^(B3) R^(A22)C(CH₃)₂ L_(A220) R^(B3) R^(A28) C(CH₃)₂ L_(A221) R^(B4) R^(A2) C(CH₃)₂L_(A222) R^(B4) R^(A3) C(CH₃)₂ L_(A223) R^(B4) R^(A14) C(CH₃)₂ L_(A224)R^(B4) R^(A22) C(CH₃)₂ L_(A225) R^(B4) R^(A28) C(CH₃)₂ L_(A226) H R^(A2)NCH₃ L_(A227) R^(A2) R^(A2) NCH₃ L_(A228) R^(A3) R^(A2) NCH₃ L_(A229)R^(A14) R^(A2) NCH₃ L_(A230) R^(A22) R^(A2) NCH₃ L_(A231) R^(A28) R^(A2)NCH₃ L_(A232) H R^(A3) NCH₃ L_(A233) R^(A2) R^(A3) NCH₃ L_(A234) R^(A3)R^(A3) NCH₃ L_(A235) R^(A14) R^(A3) NCH₃ L_(A236) R^(A22) R^(A3) NCH₃L_(A237) R^(A28) R^(A3) NCH₃ L_(A238) H R^(A14) NCH₃ L_(A239) R^(A2)R^(A14) NCH₃ L_(A240) R^(A3) R^(A14) NCH₃ L_(A241) R^(A14) R^(A14) NCH₃L_(A242) R^(A22) R^(A14) NCH₃ L_(A243) R^(A28) R^(A14) NCH₃ L_(A244) HR^(A22) NCH₃ L_(A245) R^(A2) R^(A22) NCH₃ L_(A246) R^(A3) R^(A22) NCH₃L_(A247) R^(A14) R^(A22) NCH₃ L_(A248) R^(A22) R^(A22) NCH₃ L_(A249)R^(A28) R^(A22) NCH₃ L_(A250) H R^(A28) NCH₃ L_(A251) R^(A2) R^(A28)NCH₃ L_(A252) R^(A3) R^(A28) NCH₃ L_(A253) R^(A14) R^(A28) NCH₃ L_(A254)R^(A22) R^(A28) NCH₃ L_(A255) R^(A28) R^(A28) NCH₃ L_(A256) R^(A2) HNCH₃ L_(A257) R^(A3) H NCH₃ L_(A258) R^(A14) H NCH₃ L_(A259) R^(A22) HNCH₃ L_(A260) R^(A28) H NCH₃ L_(A261) R^(A2) R^(B1) NCH₃ L_(A262) R^(A3)R^(B1) NCH₃ L_(A263) R^(A14) R^(B1) NCH₃ L_(A264) R^(A22) R^(B1) NCH₃L_(A265) R^(A28) R^(B1) NCH₃ L_(A266) R^(A2) R^(B2) NCH₃ L_(A267) R^(A3)R^(B2) NCH₃ L_(A268) R^(A14) R^(B2) NCH₃ L_(A269) R^(A22) R^(B2) NCH₃L_(A270) R^(A28) R^(B2) NCH₃ L_(A271) R^(A2) R^(B3) NCH₃ L_(A272) R^(A3)R^(B3) NCH₃ L_(A273) R^(A14) R^(B3) NCH₃ L_(A274) R^(A22) R^(B3) NCH₃L_(A275) R^(A28) R^(B3) NCH₃ L_(A276) R^(A2) R^(B4) NCH₃ L_(A277) R^(A3)R^(B4) NCH₃ L_(A278) R^(A14) R^(B4) NCH₃ L_(A279) R^(A22) R^(B4) NCH₃L_(A280) R^(A28) R^(B4) NCH₃ L_(A281) R^(A2) R^(B1) NCH₃ L_(A282) R^(A3)R^(B1) NCH₃ L_(A283) R^(A14) R^(B1) NCH₃ L_(A284) R^(A22) R^(B1) NCH₃L_(A285) R^(A28) R^(B1) NCH₃ L_(A286) R^(A2) R^(B2) NCH₃ L_(A287) R^(A3)R^(B2) NCH₃ L_(A288) R^(A14) R^(B2) NCH₃ L_(A289) R^(A22) R^(B2) NCH₃L_(A290) R^(A28) R^(B2) NCH₃ L_(A291) R^(A2) R^(B3) NCH₃ L_(A292) R^(A3)R^(B3) NCH₃ L_(A293) R^(A14) R^(B3) NCH₃ L_(A294) R^(A22) R^(B3) NCH₃L_(A295) R^(A28) R^(B3) NCH₃ L_(A296) R^(A2) R^(B4) NCH₃ L_(A297) R^(A3)R^(B4) NCH₃ L_(A298) R^(A14) R^(B4) NCH₃ L_(A299) R^(A22) R^(B4) NCH₃L_(A300) R^(A28) R^(B4) NCH₃ L_(A301) H R^(A2) N(isobutyl) L_(A302)R^(A2) R^(A2) N(isobutyl) L_(A303) R^(A3) R^(A2) N(isobutyl) L_(A304)R^(A14) R^(A2) N(isobutyl) L_(A305) R^(A22) R^(A2) N(isobutyl) L_(A306)R^(A28) R^(A2) N(isobutyl) L_(A307) H R^(A3) N(isobutyl) L_(A308) R^(A2)R^(A3) N(isobutyl) L_(A309) R^(A3) R^(A3) N(isobutyl) L_(A310) R^(A14)R^(A3) N(isobutyl) L_(A311) R^(A22) R^(A3) N(isobutyl) L_(A312) R^(A28)R^(A3) N(isobutyl) L_(A313) H R^(A14) N(isobutyl) L_(A314) R^(A2)R^(A14) N(isobutyl) L_(A315) R^(A3) R^(A14) N(isobutyl) L_(A316) R^(A14)R^(A14) N(isobutyl) L_(A317) R^(A22) R^(A14) N(isobutyl) L_(A318)R^(A28) R^(A14) N(isobutyl) L_(A319) H R^(A22) N(isobutyl) L_(A320)R^(A2) R^(A22) N(isobutyl) L_(A321) R^(A3) R^(A22) N(isobutyl) L_(A322)R^(A14) R^(A22) N(isobutyl) L_(A323) R^(A22) R^(A22) N(isobutyl)L_(A324) R^(A28) R^(A22) N(isobutyl) L_(A325) H R^(A28) N(isobutyl)L_(A326) R^(A2) R^(A28) N(isobutyl) L_(A327) R^(A3) R^(A28) N(isobutyl)L_(A328) R^(A14) R^(A28) N(isobutyl) L_(A329) R^(A22) R^(A28)N(isobutyl) L_(A330) R^(A28) R^(A28) N(isobutyl) L_(A331) R^(A2) HN(isobutyl) L_(A332) R^(A3) H N(isobutyl) L_(A333) R^(A14) H N(isobutyl)L_(A334) R^(A22) H N(isobutyl) L_(A335) R^(A28) H N(isobutyl) L_(A336)R^(A2) R^(B1) N(isobutyl) L_(A337) R^(A3) R^(B1) N(isobutyl) L_(A338)R^(A14) R^(B1) N(isobutyl) L_(A339) R^(A22) R^(B1) N(isobutyl) L_(A340)R^(A28) R^(B1) N(isobutyl) L_(A341) R^(A2) R^(B2) N(isobutyl) L_(A342)R^(A3) R^(B2) N(isobutyl) L_(A343) R^(A14) R^(B2) N(isobutyl) L_(A344)R^(A22) R^(B2) N(isobutyl) L_(A345) R^(A28) R^(B2) N(isobutyl) L_(A346)R^(A2) R^(B3) N(isobutyl) L_(A347) R^(A3) R^(B3) N(isobutyl) L_(A348)R^(A14) R^(B3) N(isobutyl) L_(A349) R^(A22) R^(B3) N(isobutyl) L_(A350)R^(A28) R^(B3) N(isobutyl) L_(A351) R^(A2) R^(B4) N(isobutyl) L_(A352)R^(A3) R^(B4) N(isobutyl) L_(A353) R^(A14) R^(B4) N(isobutyl) L_(A354)R^(A22) R^(B4) N(isobutyl) L_(A355) R^(A28) R^(B4) N(isobutyl) L_(A356)R^(B1) R^(A2) N(isobutyl) L_(A357) R^(B1) R^(A3) N(isobutyl) L_(A358)R^(B1) R^(A14) N(isobutyl) L_(A359) R^(B1) R^(A22) N(isobutyl) L_(A360)R^(B1) R^(A28) N(isobutyl) L_(A361) R^(B2) R^(A2) N(isobutyl) L_(A362)R^(B2) R^(A3) N(isobutyl) L_(A363) R^(B2) R^(A14) N(isobutyl) L_(A364)R^(B2) R^(A22) N(isobutyl) L_(A365) R^(B2) R^(A28) N(isobutyl) L_(A366)R^(B3) R^(A2) N(isobutyl) L_(A367) R^(B3) R^(A3) N(isobutyl) L_(A368)R^(B3) R^(A14) N(isobutyl) L_(A369) R^(B3) R^(A22) N(isobutyl) L_(A370)R^(B3) R^(A28) N(isobutyl) L_(A371) R^(B4) R^(A2) N(isobutyl) L_(A372)R^(B4) R^(A3) N(isobutyl) L_(A373) R^(B4) R^(A14) N(isobutyl) L_(A374)R^(B4) R^(A22) N(isobutyl) L_(A375) R^(B4) R^(A28) N(isobutyl)

and L_(A376) through L_(A750) are based on a structure of Formula V,

in which R³, R⁴, and X are defined as: Ligand R³ R⁴ X L_(A376) H R^(A2)O L_(A377) R^(A2) R^(A2) O L_(A378) R^(A3) R^(A2) O L_(A379) R^(A14)R^(A2) O L_(A380) R^(A22) R^(A2) O L_(A381) R^(A28) R^(A2) O L_(A382) HR^(A3) O L_(A383) R^(A2) R^(A3) O L_(A384) R^(A3) R^(A3) O L_(A385)R^(A14) R^(A3) O L_(A386) R^(A22) R^(A3) O L_(A387) R^(A28) R^(A3) OL_(A388) H R^(A14) O L_(A389) R^(A2) R^(A14) O L_(A390) R^(A3) R^(A14) OL_(A391) R^(A14) R^(A14) O L_(A392) R^(A22) R^(A14) O L_(A393) R^(A28)R^(A14) O L_(A394) H R^(A22) O L_(A395) R^(A2) R^(A22) O L_(A396) R^(A3)R^(A22) O L_(A397) R^(A14) R^(A22) O L_(A398) R^(A22) R^(A22) O L_(A399)R^(A28) R^(A22) O L_(A400) H R^(A28) O L_(A401) R^(A2) R^(A28) OL_(A402) R^(A3) R^(A28) O L_(A403) R^(A14) R^(A28) O L_(A404) R^(A22)R^(A28) O L_(A405) R^(A28) R^(A28) O L_(A406) R^(A2) H O L_(A407) R^(A3)H O L_(A408) R^(A14) H O L_(A409) R^(A22) H O L_(A410) R^(A28) H OL_(A411) R^(A2) R^(B1) O L_(A412) R^(A3) R^(B1) O L_(A413) R^(A14)R^(B1) O L_(A414) R^(A22) R^(B1) O L_(A415) R^(A28) R^(B1) O L_(A416)R^(A2) R^(B2) O L_(A417) R^(A3) R^(B2) O L_(A418) R^(A14) R^(B2) OL_(A419) R^(A22) R^(B2) O L_(A420) R^(A28) R^(B2) O L_(A421) R^(A2)R^(B3) O L_(A422) R^(A3) R^(B3) O L_(A423) R^(A14) R^(B3) O L_(A424)R^(A22) R^(B3) O L_(A425) R^(A28) R^(B3) O L_(A426) R^(A2) R^(B4) OL_(A427) R^(A3) R^(B4) O L_(A428) R^(A14) R^(B4) O L_(A429) R^(A22)R^(B4) O L_(A430) R^(A28) R^(B4) O L_(A431) R^(B1) R^(A2) O L_(A432)R^(B1) R^(A3) O L_(A433) R^(B1) R^(A14) O L_(A434) R^(B1) R^(A22) OL_(A435) R^(B1) R^(A28) O L_(A436) R^(B2) R^(A2) O L_(A437) R^(B2)R^(A3) O L_(A438) R^(B2) R^(A14) O L_(A439) R^(B2) R^(A22) O L_(A440)R^(B2) R^(A28) O L_(A441) R^(B3) R^(A2) O L_(A442) R^(B3) R^(A3) OL_(A443) R^(B3) R^(A14) O L_(A444) R^(B3) R^(A22) O L_(A445) R^(B3)R^(A28) O L_(A446) R^(B4) R^(A2) O L_(A447) R^(B4) R^(A3) O L_(A448)R^(B4) R^(A14) O L_(A449) R^(B4) R^(A22) O L_(A450) R^(B4) R^(A28) OL_(A451) H R^(A2) S L_(A452) R^(A2) R^(A2) S L_(A453) R^(A3) R^(A2) SL_(A454) R^(A14) R^(A2) S L_(A455) R^(A22) R^(A2) S L_(A456) R^(A28)R^(A2) S L_(A457) H R^(A3) S L_(A458) R^(A2) R^(A3) S L_(A459) R^(A3)R^(A3) S L_(A460) R^(A14) R^(A3) S L_(A461) R^(A22) R^(A3) S L_(A462)R^(A28) R^(A3) S L_(A463) H R^(A14) S L_(A464) R^(A2) R^(A14) S L_(A465)R^(A3) R^(A14) S L_(A466) R^(A14) R^(A14) S L_(A467) R^(A22) R^(A14) SL_(A468) R^(A28) R^(A14) S L_(A469) H R^(A22) S L_(A470) R^(A2) R^(A22)S L_(A471) R^(A3) R^(A22) S L_(A472) R^(A14) R^(A22) S L_(A473) R^(A22)R^(A22) S L_(A474) R^(A28) R^(A22) S L_(A475) H R^(A28) S L_(A476)R^(A2) R^(A28) S L_(A477) R^(A3) R^(A28) S L_(A478) R^(A14) R^(A28) SL_(A479) R^(A22) R^(A28) S L_(A480) R^(A28) R^(A28) S L_(A481) R^(A2) HS L_(A482) R^(A3) H S L_(A483) R^(A14) H S L_(A484) R^(A22) H S L_(A485)R^(A28) H S L_(A486) R^(A2) R^(B1) S L_(A487) R^(A3) R^(B1) S L_(A488)R^(A14) R^(B1) S L_(A489) R^(A22) R^(B1) S L_(A490) R^(A28) R^(B1) SL_(A491) R^(A2) R^(B2) S L_(A492) R^(A3) R^(B2) S L_(A493) R^(A14)R^(B2) S L_(A494) R^(A22) R^(B2) S L_(A495) R^(A28) R^(B2) S L_(A496)R^(A2) R^(B3) S L_(A497) R^(A3) R^(B3) S L_(A498) R^(A14) R^(B3) SL_(A499) R^(A22) R^(B3) S L_(A500) R^(A28) R^(B3) S L_(A501) R^(A2)R^(B4) S L_(A502) R^(A3) R^(B4) S L_(A503) R^(A14) R^(B4) S L_(A504)R^(A22) R^(B4) S L_(A505) R^(A28) R^(B4) S L_(A506) R^(B1) R^(A2) SL_(A507) R^(B1) R^(A3) S L_(A508) R^(B1) R^(A14) S L_(A509) R^(B1)R^(A22) S L_(A510) R^(B1) R^(A28) S L_(A511) R^(B2) R^(A2) S L_(A512)R^(B2) R^(A3) S L_(A513) R^(B2) R^(A14) S L_(A514) R^(B2) R^(A22) SL_(A515) R^(B2) R^(A28) S L_(A516) R^(B3) R^(A2) S L_(A517) R^(B3)R^(A3) S L_(A518) R^(B3) R^(A14) S L_(A519) R^(B3) R^(A22) S L_(A520)R^(B3) R^(A28) S L_(A521) R^(B4) R^(A2) S L_(A522) R^(B4) R^(A3) SL_(A523) R^(B4) R^(A14) S L_(A524) R^(B4) R^(A22) S L_(A525) R^(B4)R^(A28) S L_(A526) H R^(A2) C(CH₃)₂ L_(A527) R^(A2) R^(A2) C(CH₃)₂L_(A528) R^(A3) R^(A2) C(CH₃)₂ L_(A529) R^(A14) R^(A2) C(CH₃)₂ L_(A530)R^(A22) R^(A2) C(CH₃)₂ L_(A531) R^(A28) R^(A2) C(CH₃)₂ L_(A532) H R^(A3)C(CH₃)₂ L_(A533) R^(A2) R^(A3) C(CH₃)₂ L_(A534) R^(A3) R^(A3) C(CH₃)₂L_(A535) R^(A14) R^(A3) C(CH₃)₂ L_(A536) R^(A22) R^(A3) C(CH₃)₂ L_(A537)R^(A28) R^(A3) C(CH₃)₂ L_(A538) H R^(A14) C(CH₃)₂ L_(A539) R^(A2)R^(A14) C(CH₃)₂ L_(A540) R^(A3) R^(A14) C(CH₃)₂ L_(A541) R^(A14) R^(A14)C(CH₃)₂ L_(A542) R^(A22) R^(A14) C(CH₃)₂ L_(A543) R^(A28) R^(A14)C(CH₃)₂ L_(A544) H R^(A22) C(CH₃)₂ L_(A545) R^(A2) R^(A22) C(CH₃)₂L_(A546) R^(A3) R^(A22) C(CH₃)₂ L_(A547) R^(A14) R^(A22) C(CH₃)₂L_(A548) R^(A22) R^(A22) C(CH₃)₂ L_(A549) R^(A28) R^(A22) C(CH₃)₂L_(A550) H R^(A28) C(CH₃)₂ L_(A551) R^(A2) R^(A28) C(CH₃)₂ L_(A552)R^(A3) R^(A28) C(CH₃)₂ L_(A553) R^(A14) R^(A28) C(CH₃)₂ L_(A554) R^(A22)R^(A28) C(CH₃)₂ L_(A555) R^(A28) R^(A28) C(CH₃)₂ L_(A556) R^(A2) HC(CH₃)₂ L_(A557) R^(A3) H C(CH₃)₂ L_(A558) R^(A14) H C(CH₃)₂ L_(A559)R^(A22) H C(CH₃)₂ L_(A560) R^(A28) H C(CH₃)₂ L_(A561) R^(A2) R^(B1)C(CH₃)₂ L_(A562) R^(A3) R^(B1) C(CH₃)₂ L_(A563) R^(A14) R^(B1) C(CH₃)₂L_(A564) R^(A22) R^(B1) C(CH₃)₂ L_(A565) R^(A28) R^(B1) C(CH₃)₂ L_(A566)R^(A2) R^(B2) C(CH₃)₂ L_(A567) R^(A3) R^(B2) C(CH₃)₂ L_(A568) R^(A14)R^(B2) C(CH₃)₂ L_(A569) R^(A22) R^(B2) C(CH₃)₂ L_(A570) R^(A28) R^(B2)C(CH₃)₂ L_(A571) R^(A2) R^(B3) C(CH₃)₂ L_(A572) R^(A3) R^(B3) C(CH₃)₂L_(A573) R^(A14) R^(B3) C(CH₃)₂ L_(A574) R^(A22) R^(B3) C(CH₃)₂ L_(A575)R^(A28) R^(B3) C(CH₃)₂ L_(A576) R^(A2) R^(B4) C(CH₃)₂ L_(A577) R^(A3)R^(B4) C(CH₃)₂ L_(A578) R^(A14) R^(B4) C(CH₃)₂ L_(A579) R^(A22) R^(B4)C(CH₃)₂ L_(A580) R^(A28) R^(B4) C(CH₃)₂ L_(A581) R^(B1) R^(A2) C(CH₃)₂L_(A582) R^(B1) R^(A3) C(CH₃)₂ L_(A583) R^(B1) R^(A14) C(CH₃)₂ L_(A584)R^(B1) R^(A22) C(CH₃)₂ L_(A585) R^(B1) R^(A28) C(CH₃)₂ L_(A586) R^(B2)R^(A2) C(CH₃)₂ L_(A587) R^(B2) R^(A3) C(CH₃)₂ L_(A588) R^(B2) R^(A14)C(CH₃)₂ L_(A589) R^(B2) R^(A22) C(CH₃)₂ L_(A590) R^(B2) R^(A28) C(CH₃)₂L_(A591) R^(B3) R^(A2) C(CH₃)₂ L_(A592) R^(B3) R^(A3) C(CH₃)₂ L_(A593)R^(B3) R^(A14) C(CH₃)₂ L_(A594) R^(B3) R^(A22) C(CH₃)₂ L_(A595) R^(B3)R^(A28) C(CH₃)₂ L_(A596) R^(B4) R^(A2) C(CH₃)₂ L_(A597) R^(B4) R^(A3)C(CH₃)₂ L_(A598) R^(B4) R^(A14) C(CH₃)₂ L_(A599) R^(B4) R^(A22) C(CH₃)₂L_(A600) R^(B4) R^(A28) C(CH₃)₂ L_(A601) H R^(A2) NCH₃ L_(A602) R^(A2)R^(A2) NCH₃ L_(A603) R^(A3) R^(A2) NCH₃ L_(A604) R^(A14) R^(A2) NCH₃L_(A605) R^(A22) R^(A2) NCH₃ L_(A606) R^(A28) R^(A2) NCH₃ L_(A607) HR^(A3) NCH₃ L_(A608) R^(A2) R^(A3) NCH₃ L_(A609) R^(A3) R^(A3) NCH₃L_(A610) R^(A14) R^(A3) NCH₃ L_(A611) R^(A22) R^(A3) NCH₃ L_(A612)R^(A28) R^(A3) NCH₃ L_(A613) H R^(A14) NCH₃ L_(A614) R^(A2) R^(A14) NCH₃L_(A615) R^(A3) R^(A14) NCH₃ L_(A616) R^(A14) R^(A14) NCH₃ L_(A617)R^(A22) R^(A14) NCH₃ L_(A618) R^(A28) R^(A14) NCH₃ L_(A619) H R^(A22)NCH₃ L_(A620) R^(A2) R^(A22) NCH₃ L_(A621) R^(A3) R^(A22) NCH₃ L_(A622)R^(A14) R^(A22) NCH₃ L_(A623) R^(A22) R^(A22) NCH₃ L_(A624) R^(A28)R^(A22) NCH₃ L_(A625) H R^(A28) NCH₃ L_(A626) R^(A2) R^(A28) NCH₃L_(A627) R^(A3) R^(A28) NCH₃ L_(A628) R^(A14) R^(A28) NCH₃ L_(A629)R^(A22) R^(A28) NCH₃ L_(A630) R^(A28) R^(A28) NCH₃ L_(A631) R^(A2) HNCH₃ L_(A632) R^(A3) H NCH₃ L_(A633) R^(A14) H NCH₃ L_(A634) R^(A22) HNCH₃ L_(A635) R^(A28) H NCH₃ L_(A636) R^(A2) R^(B1) NCH₃ L_(A637) R^(A3)R^(B1) NCH₃ L_(A638) R^(A14) R^(B1) NCH₃ L_(A639) R^(A22) R^(B1) NCH₃L_(A640) R^(A28) R^(B1) NCH₃ L_(A641) R^(A2) R^(B2) NCH₃ L_(A642) R^(A3)R^(B2) NCH₃ L_(A643) R^(A14) R^(B2) NCH₃ L_(A644) R^(A22) R^(B2) NCH₃L_(A645) R^(A28) R^(B2) NCH₃ L_(A646) R^(A2) R^(B3) NCH₃ L_(A647) R^(A3)R^(B3) NCH₃ L_(A648) R^(A14) R^(B3) NCH₃ L_(A649) R^(A22) R^(B3) NCH₃L_(A650) R^(A28) R^(B3) NCH₃ L_(A651) R^(A2) R^(B4) NCH₃ L_(A652) R^(A3)R^(B4) NCH₃ L_(A653) R^(A14) R^(B4) NCH₃ L_(A654) R^(A22) R^(B4) NCH₃L_(A655) R^(A28) R^(B4) NCH₃ L_(A656) R^(A2) R^(B1) NCH₃ L_(A657) R^(A3)R^(B1) NCH₃ L_(A658) R^(A14) R^(B1) NCH₃ L_(A659) R^(A22) R^(B1) NCH₃L_(A660) R^(A28) R^(B1) NCH₃ L_(A661) R^(A2) R^(B2) NCH₃ L_(A662) R^(A3)R^(B2) NCH₃ L_(A663) R^(A14) R^(B2) NCH₃ L_(A664) R^(A22) R^(B2) NCH₃L_(A665) R^(A28) R^(B2) NCH₃ L_(A666) R^(A2) R^(B3) NCH₃ L_(A667) R^(A3)R^(B3) NCH₃ L_(A668) R^(A14) R^(B3) NCH₃ L_(A669) R^(A22) R^(B3) NCH₃L_(A670) R^(A28) R^(B3) NCH₃ L_(A671) R^(A2) R^(B4) NCH₃ L_(A672) R^(A3)R^(B4) NCH₃ L_(A673) R^(A14) R^(B4) NCH₃ L_(A674) R^(A22) R^(B4) NCH₃L_(A675) R^(A28) R^(B4) NCH₃ L_(A676) H R^(A2) N(isobutyl) L_(A677)R^(A2) R^(A2) N(isobutyl) L_(A678) R^(A3) R^(A2) N(isobutyl) L_(A679)R^(A14) R^(A2) N(isobutyl) L_(A680) R^(A22) R^(A2) N(isobutyl) L_(A681)R^(A28) R^(A2) N(isobutyl) L_(A682) H R^(A3) N(isobutyl) L_(A683) R^(A2)R^(A3) N(isobutyl) L_(A684) R^(A3) R^(A3) N(isobutyl) L_(A685) R^(A14)R^(A3) N(isobutyl) L_(A686) R^(A22) R^(A3) N(isobutyl) L_(A687) R^(A28)R^(A3) N(isobutyl) L_(A688) H R^(A14) N(isobutyl) L_(A689) R^(A2)R^(A14) N(isobutyl) L_(A690) R^(A3) R^(A14) N(isobutyl) L_(A691) R^(A14)R^(A14) N(isobutyl) L_(A692) R^(A22) R^(A14) N(isobutyl) L_(A693)R^(A28) R^(A14) N(isobutyl) L_(A694) H R^(A22) N(isobutyl) L_(A695)R^(A2) R^(A22) N(isobutyl) L_(A696) R^(A3) R^(A22) N(isobutyl) L_(A697)R^(A14) R^(A22) N(isobutyl) L_(A698) R^(A22) R^(A22) N(isobutyl)L_(A699) R^(A28) R^(A22) N(isobutyl) L_(A700) H R^(A28) N(isobutyl)L_(A701) R^(A2) R^(A28) N(isobutyl) L_(A702) R^(A3) R^(A28) N(isobutyl)L_(A703) R^(A14) R^(A28) N(isobutyl) L_(A704) R^(A22) R^(A28)N(isobutyl) L_(A705) R^(A28) R^(A28) N(isobutyl) L_(A706) R^(A2) HN(isobutyl) L_(A707) R^(A3) H N(isobutyl) L_(A708) R^(A14) H N(isobutyl)L_(A709) R^(A22) H N(isobutyl) L_(A710) R^(A28) H N(isobutyl) L_(A711)R^(A2) R^(B1) N(isobutyl) L_(A712) R^(A3) R^(B1) N(isobutyl) L_(A713)R^(A14) R^(B1) N(isobutyl) L_(A714) R^(A22) R^(B1) N(isobutyl) L_(A715)R^(A28) R^(B1) N(isobutyl) L_(A716) R^(A2) R^(B2) N(isobutyl) L_(A717)R^(A3) R^(B2) N(isobutyl) L_(A718) R^(A14) R^(B2) N(isobutyl) L_(A719)R^(A22) R^(B2) N(isobutyl) L_(A720) R^(A28) R^(B2) N(isobutyl) L_(A721)R^(A2) R^(B3) N(isobutyl) L_(A722) R^(A3) R^(B3) N(isobutyl) L_(A723)R^(A14) R^(B3) N(isobutyl) L_(A724) R^(A22) R^(B3) N(isobutyl) L_(A725)R^(A28) R^(B3) N(isobutyl) L_(A726) R^(A2) R^(B4) N(isobutyl) L_(A727)R^(A3) R^(B4) N(isobutyl) L_(A728) R^(A14) R^(B4) N(isobutyl) L_(A729)R^(A22) R^(B4) N(isobutyl) L_(A730) R^(A28) R^(B4) N(isobutyl) L_(A731)R^(B1) R^(A2) N(isobutyl) L_(A732) R^(B1) R^(A3) N(isobutyl) L_(A733)R^(B1) R^(A14) N(isobutyl) L_(A734) R^(B1) R^(A22) N(isobutyl) L_(A735)R^(B1) R^(A28) N(isobutyl) L_(A736) R^(B2) R^(A2) N(isobutyl) L_(A737)R^(B2) R^(A3) N(isobutyl) L_(A738) R^(B2) R^(A14) N(isobutyl) L_(A739)R^(B2) R^(A22) N(isobutyl) L_(A740) R^(B2) R^(A28) N(isobutyl) L_(A741)R^(B3) R^(A2) N(isobutyl) L_(A742) R^(B3) R^(A3) N(isobutyl) L_(A743)R^(B3) R^(A14) N(isobutyl) L_(A744) R^(B3) R^(A22) N(isobutyl) L_(A745)R^(B3) R^(A28) N(isobutyl) L_(A746) R^(B4) R^(A2) N(isobutyl) L_(A747)R^(B4) R^(A3) N(isobutyl) L_(A748) R^(B4) R^(A14) N(isobutyl) L_(A749)R^(B4) R^(A22) N(isobutyl) L_(A750) R^(B4) R^(A28) N(isobutyl)

wherein R^(B1) to R^(B4) have the following structures:


12. The compound of claim 1, wherein the compound has a structure ofFormula III, (L_(A))_(n)Ir(L_(B))_(3-n), wherein L_(B) is a bidentateligand and n is 1, 2, or
 3. 13. The compound of claim 12, wherein theligand L_(B) is selected from the group consisting of:


14. The compound of claim 11, wherein the compound is selected from thegroup consisting of Compound 1 through Compound 12,750; wherein eachCompound x has the formula Ir(L_(Ak))₂(L_(Bj)); wherein x=750j+k−750, kis an integer from 1 to 750, and j is an integer from 1 to 17; andwherein ligands L_(B1) through L_(B17) are defined as follows:


15. A first device comprising a first organic light emitting device, thefirst organic light emitting device comprising: an anode; a cathode; andan organic layer, disposed between the anode and the cathode, comprisinga compound comprising a ligand L_(A) of Formula I:

wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclicring; wherein R is fused to ring B and has a structure of Formula II:

wherein the wave lines indicate bonds to ring B; wherein R¹ representsmono, di, tri, or tetra substitution, or no substitution; wherein R²represents mono or di substitution, or no substitution; wherein X¹, X²,X³, and X⁴ are each independently carbon or nitrogen; wherein at leasttwo adjacent of X¹, X², X³, and X⁴ are carbon and fuse to R; wherein Xis selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O,S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; wherein R¹, R², R³, R⁴, R′, and R″are each independently selected from the group consisting of hydrogen,deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof; and wherein any two adjacent substituents are optionally joinedto form into a ring; wherein at least one of R³ and R⁴ comprises achemical group selected from the group consisting of alkyl, cycloalkyl,partially fluorinated alkyl, partially fluorinated cycloalkyl, andcombinations thereof; wherein L_(A) is coordinated to a metal M; whereinL_(A) is optionally linked with other ligands to comprise a tridentate,tetradentate, pentadentate, or hexadentate ligand; and wherein M isoptionally coordinated to other ligands.
 16. The first device of claim15, wherein the first device is selected from the group consisting of aconsumer product, an electronic component module, an organiclight-emitting device, and a lighting panel.
 17. The first device ofclaim 15, wherein the organic layer is an emissive layer and thecompound is an emissive dopant or a non-emissive dopant.
 18. The firstdevice of claim 15, wherein the organic layer further comprises a host,wherein host comprises at least one chemical group selected from thegroup consisting of carbazole, dibenzothiophene, dibenzofuran,dibenzoselenophene, azacarbazole, aza-dibenzothiophene,aza-dibenzofuran, and aza-dibenzoselenophene.
 19. The first device ofclaim 15, wherein the organic layer further comprises a host, whereinthe host is selected from the group consisting of:

and combinations thereof.
 20. A formulation comprising a compoundcomprising a ligand L_(A) of Formula I:

wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclicring; wherein R is fused to ring B and has a structure of Formula II:

wherein the wave lines indicate bonds to ring B; wherein R¹ representsmono, di, tri, or tetra substitution, or no substitution; wherein R²represents mono or di substitution, or no substitution; wherein X¹, X²,X³, and X⁴ are each independently carbon or nitrogen; wherein at leasttwo adjacent of X¹, X², X³, and X⁴ are carbon and fuse to R; wherein Xis selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O,S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; wherein R¹, R², R³, R⁴, R′, and R″are each independently selected from the group consisting of hydrogen,deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof; and wherein any two adjacent substituents are optionally joinedto form into a ring; wherein at least one of R³ and R⁴ comprises achemical group selected from the group consisting of alkyl, cycloalkyl,partially fluorinated alkyl, partially fluorinated cycloalkyl, andcombinations thereof; wherein the ligand L_(A) is coordinated to a metalM; wherein the ligand L_(A) is optionally linked with other ligands tocomprise a tridentate, tetradentate, pentadentate, or hexadentateligand; and wherein M is optionally coordinated to other ligands.